Piperazine derivatives and their use in controlling pests

ABSTRACT

The use of a compound of formula I 
                         
wherein Y is a single bond, C═O, C═S or S(O) m  where m is 0, 1 or 2;
 
the ring
 
                         
is a 6-membered aromatic or is a 5 or 6 membered heteroaromatic ring; Ra, R 1 , R 2 , R 4  and R 8  are specified organic groups; n and p are independently 0-4; or salts or N-oxides thereof or compositions containing them in controlling insects, acarines, nematodes or molluscs. Novel compounds are also provided.

This application is a divisional application of U.S. Ser. No. 11/569,006filed Jul. 26, 2007, which is a 371 of International Application No.PCT/IB2005/001468 filed May 12, 2005, which claims priority to GB0412072.0 filed May 28, 2004, the contents of which are incorporatedherein by reference.

The present invention relates to piperazine derivatives, to processesfor preparing them, to insecticidal, acaricidal, molluscicidal andnematicidal compositions comprising them and to methods of using them tocombat and control insect, acarine, mollusc and nematode pests.

Piperazine derivatives with antiprotazoal properties are disclosed infor example in US331845 and EP103464 discloses pyrimidinyl piperazinecompounds with antibacterial properties.

It has now surprisingly been found that certain piperazines haveinsecticidal properties.

The present invention therefore provides a method of combating andcontrolling insects, acarines, nematodes or molluscs which comprisesapplying to a pest, to a locus of a pest, or to a plant susceptible toattack by a pest an insecticidally, acaricidally, nematicidally ormolluscicidally effective amount of a compound of formula (I):

Y is a single bond, C═O, C═S or S(O)_(m) where m is 0, 1 or 2;

the ring

is a 6 membered aromatic ring or is a 5 or 6 membered heteroaromaticring;

R¹ is hydrogen, optionally substituted alkyl, optionally substitutedalkoxycarbonyl, optionally substituted alkylcarbonyl, aminocarbonyl,optionally substituted alkylaminocarbonyl, optionally substituteddialkylaminocarbonyl, optionally substituted aryl, optionallysubstituted heteroaryl, optionally substituted alkoxy, optionallysubstituted aryloxy, optionally substituted heteroaryloxy, optionallysubstituted heterocyclyloxy, cyano, optionally substituted alkenyl,optionally substituted alkynyl, optionally substituted cycloalkyl,optionally substituted cycloalkenyl, formyl, optionally substitutedheterocyclyl, optionally substituted alkylthio, NO or NR¹³R¹⁴ where R¹³and R¹⁴ are independently hydrogen, COR¹⁵, optionally substituted alkyl,optionally substituted aryl, optionally substituted heteroaryl,optionally substituted heterocyclyl or R¹³ and R¹⁴ together with the Natom to which they are attached form a group —N═C(R¹⁶)—NR¹⁷R¹⁸ or R¹³and R¹⁴ together with the N atom to which they are attached form a five,six or seven-membered heterocyclic ring which may contain one or twofurther heteroatoms selected from O, N or S and which may be optionallysubstituted by one or two C₁₋₆ alkyl groups; R¹⁵ is H, optionallysubstituted alkyl, optionally substituted alkoxy, optionally substitutedaryl, optionally substituted aryloxy optionally substituted heteroaryl,optionally substituted heteroaryloxy or NR¹⁹R²⁰; R¹⁶, R¹⁷ and R¹⁸ areeach independently H or lower alkyl; R¹⁹ and R²⁰ are independentlyoptionally substituted alkyl, optionally substituted aryl or optionallysubstituted heteroaryl;

R² is H, hydroxy, optionally substituted alkoxy or optionallysubstituted alkyl; or R¹ and R² together with the groups Y and N form a5- or 6-membered heterocyclic ring which may optionally contain onefurther heteroatom selected from O, N or S and which may be optionallysubstituted by C₁₋₄ alkyl, C₁₋₄ haloalkyl or halogen;

each R⁴ is independently halogen, nitro, cyano, optionally substitutedC₁₋₈ alkyl, optionally substituted C₂₋₆ alkenyl, optionally substitutedC₂₋₆ alkynyl, optionally substituted alkoxycarbonyl, optionallysubstituted alkylcarbonyl, optionally substituted alkylaminocarbonyl,optionally substituted dialkylaminocarbonyl, optionally substituted C₃₋₇cycloalkyl, optionally substituted aryl, optionally substitutedheteroaryl, optionally substituted heterocyclyl, optionally substitutedalkoxy, optionally substituted aryloxy, optionally substitutedheteroaryloxy, optionally substituted alkylthio or R²¹R²²N where R²¹ andR²² are, independently, hydrogen, C₁₋₈ alkyl, C₃₋₇ cycloalkyl, C₃₋₆alkenyl, C₃₋₆ alkynyl, C₃₋₇ cycloalkyl(C₁₋₄)alkyl, C₂₋₆ haloalkyl, C₁₋₆alkoxy(C₁₋₆)alkyl, C₁₋₆ alkoxycarbonyl or R²¹ and R²² together with theN atom to which they are attached form a five, six or seven-memberedheterocyclic ring which may contain one or two further heteroatomsselected from O, N or S and which may be optionally substituted by oneor two C₁₋₆ alkyl groups, or 2 adjacent groups R⁴ together with thecarbon atoms to which they are attached form a 4, 5, 6, or 7 memberedcarbocyclic or heterocyclic ring which may be optionally substituted byhalogen; n is 0, 1, 2, 3 or 4;

R⁸ is optionally substituted alkyl, optionally substituted alkenyl,optionally substituted alkynyl, optionally substituted cycloalkyl,optionally substituted aryl, optionally substituted alkoxy, optionallysubstituted aryloxy, optionally substituted alkoxycarbonyl, optionallysubstituted alkylcarbonyl or optionally substituted alkenylcarbonyl;

each Ra is independently halogen, hydroxy, cyano, optionally substitutedC₁₋₈ alkyl, optionally substituted C₂₋₆ alkenyl, optionally substitutedC₂₋₆ alkynyl, optionally substituted alkoxycarbonyl, optionallysubstituted alkylcarbonyl, optionally substituted alkylaminocarbonyl,optionally substituted dialkylaminocarbonyl, optionally substituted C₃₋₇cycloalkyl, optionally substituted aryl, optionally substitutedheteroaryl, optionally substituted heterocyclyl, optionally substitutedalkoxy, optionally substituted aryloxy, optionally substitutedheteroaryloxy, optionally substituted alkylthio, optionally substitutedarylthio or R²³R²⁴N where R²³ and R²⁴ are, independently, hydrogen, C₁₋₈alkyl, C₃₋₇ cycloalkyl, C₃₋₆ alkenyl, C₃₋₆ alkynyl, C₃₋₇cycloalkyl(C₁₋₄)alkyl, C₂₋₆ haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₁₋₆alkoxycarbonyl or R²³ and R²⁴ together with the N atom to which they areattached form a five, six or seven-membered heterocyclic ring which maycontain one or two further heteroatoms selected from O, N or S and whichmay be optionally substituted by one or two C₁₋₆ alkyl groups, or two Ragroups attached to the same carbon atom are ═O, ═S, ═NRb, ═CRcRd whereRb, Rc and Rd are independently H or optionally substituted alkyl; p is0, 1, 2, 3 or 4 or salts or N-oxides thereof.

The compounds of formula (I) may exist in different geometric or opticalisomers or tautomeric forms. This invention covers all such isomers andtautomers and mixtures thereof in all proportions as well as isotopicforms such as deuterated compounds.

Each alkyl moiety either alone or as part of a larger group (such asalkoxy, alkoxycarbonyl, alkylcarbonyl, alkylaminocarbonyl,dialkylaminocarbonyl) is a straight or branched chain and is, forexample, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl,iso-propyl, n-butyl, sec-butyl, iso-butyl, tert-butyl or neo-pentyl. Thealkyl groups are suitably C₁ to C₁₂ alkyl groups, but are preferablyC₁-C₁₀, more preferably C₁-C₈, even more preferably C₁-C₆ and mostpreferably C₁-C₄ alkyl groups.

When present, the optional substituents on an alkyl moiety (alone or aspart of a larger group such as alkoxy, alkoxycarbonyl, alkylcarbonyl,alkylaminocarbonyl, dialkylaminocarbonyl) include one or more ofhalogen, nitro, cyano, NCS—, C₃₋₇ cycloalkyl (itself optionallysubstituted with C₁₋₆ alkyl or halogen), C₅₋₇ cycloalkenyl (itselfoptionally substituted with C₁₋₆ alkyl or halogen), hydroxy, C₁₋₁₀alkoxy, C₁₋₁₀ alkoxy(C₁₋₁₀)alkoxy, tri(C₁₋₄)alkylsilyl(C₁₋₆)alkoxy, C₁₋₆alkoxycarbonyl(C₁₋₁₀)alkoxy, C₁₋₁₀ haloalkoxy, aryl(C₁₋₄)-alkoxy (wherethe aryl group is optionally substituted), C₃₋₇ cycloalkyloxy (where thecycloalkyl group is optionally substituted with C₁₋₆ alkyl or halogen),C₂₋₁₀ alkenyloxy, C₂₋₁₀ alkynyloxy, SH, C₁₋₁₀ alkylthio, C₁₋₁₀haloalkylthio, aryl(C₁₋₄)alkylthio (where the aryl group is optionallysubstituted), C₃₋₇ cycloalkylthio (where the cycloalkyl group isoptionally substituted with C₁₋₆ alkyl or halogen),tri(C₁₋₄)alkylsilyl(C₁₋₆)alkylthio, arylthio (where the aryl group isoptionally substituted), C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl,C₁₋₆ alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, arylsulfonyl (where the arylgroup may be optionally substituted), tri(C₁₋₄)alkylsilyl,aryldi(C₁₋₄)alkylsilyl, (C₁₋₄)alkyldiarylsilyl, triarylsilyl, C₁₋₁₀alkylcarbonyl, HO₂C, C₁₋₁₀ alkoxycarbonyl, aminocarbonyl, C₁₋₆alkylaminocarbonyl, di(C₁₋₆ alkyl)aminocarbonyl, N—(C₁₋₃ alkyl)-N—(C₁₋₃alkoxy)aminocarbonyl, C₁₋₆ alkylcarbonyloxy, arylcarbonyloxy (where thearyl group is optionally substituted), di(C₁₋₆)alkylaminocarbonyloxy,oximes such as ═NOalkyl, ═NOhaloalkyl and ═NOaryl (itself optionallysubstituted), aryl (itself optionally substituted), heteroaryl (itselfoptionally substituted), heterocyclyl (itself optionally substitutedwith C₁₋₆ alkyl or halogen), aryloxy (where the aryl group is optionallysubstituted), heteroaryloxy, (where the heteroaryl group is optionallysubstituted), heterocyclyloxy (where the heterocyclyl group isoptionally substituted with C₁₋₆ alkyl or halogen), amino, C₁₋₆alkylamino, di(C₁₋₆)alkylamino, C₁₋₆ alkylcarbonylamino,N—(C₁₋₆)alkylcarbonyl-N—(C₁₋₆)alkylamino, C₂₋₆ alkenylcarbonyl, C₂₋₆alkynylcarbonyl, C₃₋₆ alkenyloxycarbonyl, C₃₋₆ alkynyloxycarbonyl,aryloxycarbonyl (where the aryl group is optionally substituted) andarylcarbonyl (where the aryl group is optionally substituted).

Alkenyl and alkynyl moieties can be in the form of straight or branchedchains, and the alkenyl moieties, where appropriate, can be of eitherthe (E)- or (Z)-configuration. Examples are vinyl, allyl and propargyl.

When present, the optional substituents on alkenyl or alkynyl includethose optional substituents given above for an alkyl moiety.

In the context of this specification acyl is optionally substituted C₁₋₆alkylcarbonyl (for example acetyl), optionally substituted C₂₋₆alkenylcarbonyl, optionally substituted C₂₋₆ alkynylcarbonyl, optionallysubstituted arylcarbonyl (for example benzoyl) or optionally substitutedheteroarylcarbonyl.

Halogen is fluorine, chlorine, bromine or iodine.

Haloalkyl groups are alkyl groups which are substituted with one or moreof the same or different halogen atoms and are, for example, CF₃, CF₂Cl,CF₃CH₂ or CHF₂CH₂.

In the context of the present specification the terms “aryl”, “aromaticring” and “aromatic ring system” refer to ring systems which may bemono-, bi- or tricyclic. Examples of such rings include phenyl,naphthalenyl, anthracenyl, indenyl or phenanthrenyl. A preferred arylgroup is phenyl. In addition, the terms “heteroaryl”, “heteroaromaticring” or “heteroaromatic ring system” refer to an aromatic ring systemcontaining at least one heteroatom and consisting either of a singlering or of two or more fused rings. Preferably, single rings willcontain up to three and bicyclic systems up to four heteroatoms whichwill preferably be chosen from nitrogen, oxygen and sulphur. Examples ofsuch groups include furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl,1,2,3-triazolyl, 1,2,4-triazolyl, oxazolyl, isoxazolyl, thiazolyl,isothiazolyl, 1,2,3-oxadiazolyl, 1,2,4-oxadiazolyl, 1,3,4-oxadiazolyl,1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl,1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl, pyrimidinyl,pyridazinyl, pyrazinyl, 1,2,3-triazinyl, 1,2,4-triazinyl,1,3,5-triazinyl, benzofuryl, benzisofuryl, benzothienyl, benzisothienyl,indolyl, isoindolyl, indazolyl, benzothiazolyl, benzisothiazolyl,benzoxazolyl, benzisoxazolyl, benzimidazolyl, 2,1,3-benzoxadiazolequinolinyl, isoquinolinyl, cinnolinyl, phthalazinyl, quinazolinyl,quinoxalinyl, naphthyridinyl, benzotriazinyl, purinyl, pteridinyl andindolizinyl. Preferred examples of heteroaromatic radicals includepyridyl, pyrimidyl, triazinyl, thienyl, furyl, oxazolyl, isoxazolyl,2,1,3-benzoxadiazole and thiazolyl.

The terms heterocycle and heterocyclyl refer to a non-aromatic ringcontaining up to 10 atoms including one or more (preferably one or two)heteroatoms selected from O, S and N. Examples of such rings include1,3-dioxolane, tetrahydrofuran and morpholine.

When present, the optional substituents on heterocyclyl include C₁₋₆alkyl and C₁₋₆ haloalkyl as well as those optional substituents givenabove for an alkyl moiety.

Cycloalkyl includes cyclopropyl, cyclopentyl and cyclohexyl.

Cycloalkenyl includes cyclopentenyl and cyclohexenyl.

When present, the optional substituents on cycloalkyl or cycloalkenylinclude C₁₋₃ alkyl as well as those optional substituents given abovefor an alkyl moiety.

Carbocyclic rings include aryl, cycloalkyl and cycloalkenyl groups.

When present, the optional substituents on aryl or heteroaryl areselected independently, from halogen, nitro, cyano, NCS—, C₁₋₆ alkyl,C₁₋₆ haloalkyl, C₁₋₆ alkoxy-(C₁₋₆)alkyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl,C₂₋₆ alkynyl, C₃₋₇ cycloalkyl (itself optionally substituted with C₁₋₆alkyl or halogen), C₅₋₇ cycloalkenyl (itself optionally substituted withC₁₋₆ alkyl or halogen), hydroxy, C₁₋₁₀ alkoxy, C₁₋₁₀alkoxy(C₁₋₁₀)alkoxy, tri(C₁₋₄)alkylsilyl(C₁₋₆)alkoxy, C₁₋₆alkoxycarbonyl(C₁₋₁₀)alkoxy, C₁₋₁₀ haloalkoxy, aryl(C₁₋₄)alkoxy (wherethe aryl group is optionally substituted with halogen or C₁₋₆ alkyl),C₃₋₇ cycloalkyloxy (where the cycloalkyl group is optionally substitutedwith C₁₋₆ alkyl or halogen), C₂₋₁₀ alkenyloxy, C₂₋₁₀ alkynyloxy, SH,C₁₋₁₀ alkylthio, C₁₋₁₀ haloalkylthio, aryl(C₁₋₄)alkylthio C₃₋₇cycloalkylthio (where the cycloalkyl group is optionally substitutedwith C₁₋₆ alkyl or halogen), tri(C₁₋₄)-alkylsilyl(C₁₋₆)alkylthio,arylthio, C₁₋₆ alkylsulfonyl, C₁₋₆ haloalkylsulfonyl, C₁₋₆alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, arylsulfonyl,tri(C₁₋₄)alkylsilyl, aryldi(C₁₋₄)-alkylsilyl, (C₁₋₄)alkyldiarylsilyl,triarylsilyl, C₁₋₁₀ alkylcarbonyl, HO₂C, C₁₋₁₀ alkoxycarbonyl,aminocarbonyl, C₁₋₆ alkylaminocarbonyl, di(C₁₋₆ alkyl)-aminocarbonyl,N—(C₁₋₃ alkyl)-N—(C₁₋₃ alkoxy)aminocarbonyl, C₁₋₆ alkylcarbonyloxy,arylcarbonyloxy, di(C₁₋₆)alkylamino-carbonyloxy, aryl (itself optionallysubstituted with C₁₋₆ alkyl or halogen), heteroaryl (itself optionallysubstituted with C₁₋₆ alkyl or halogen), heterocyclyl (itself optionallysubstituted with C₁₋₆ alkyl or halogen), aryloxy (where the aryl groupis optionally substituted with C₁₋₆ alkyl or halogen), heteroaryloxy(where the heteroaryl group is optionally substituted with C₁₋₆ alkyl orhalogen), heterocyclyloxy (where the heterocyclyl group is optionallysubstituted with C₁₋₆ alkyl or halogen), amino, C₁₋₆ alkylamino,di(C₁₋₆)alkylamino, C₁₋₆ alkylcarbonylamino,N—(C₁₋₆)alkylcarbonyl-N—(C₁₋₆)alkylamino, arylcarbonyl, (where the arylgroup is itself optionally substituted with halogen or C₁₋₆ alkyl) ortwo adjacent positions on an aryl or heteroaryl system may be cyclisedto form a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itselfoptionally substituted with halogen or C₁₋₆ alkyl. Further substituentsfor aryl or heteroaryl include aryl carbonyl amino (where the aryl groupis substituted by C₁₋₆ alkyl or halogen), (C₁₋₆)alkyloxycarbonylamino(C₁₋₆)alkyloxycarbonyl-N—(C₁₋₆)alkylamino, aryloxycarbonylamino (wherethe aryl group is substituted by C₁₋₆ alkyl or halogen),aryloxycarbonyl-N—(C₁₋₆)alkylamino, (where the aryl group is substitutedby C₁₋₆ alkyl or halogen), arylsulphonylamino (where the aryl group issubstituted by C₁₋₆ alkyl or halogen), arylsulphonyl-N—(C₁₋₆)alkylamino(where the aryl group is substituted by C₁₋₆ alkyl or halogen),aryl-N—(C₁₋₆)alkylamino (where the aryl group is substituted by C₁₋₆alkyl or halogen), arylamino (where the aryl group is substituted byC₁₋₆ alkyl or halogen), heteroaryl amino (where the heteroaryl group issubstituted by C₁₋₆ alkyl or halogen), heterocyclylamino (where theheterocyclyl group is substituted by C₁₋₆ alkyl or halogen),aminocarbonylamino, C₁₋₆ alkylaminocarbonyl amino,di(C₁₋₆)alkylaminocarbonyl amino, arylaminocarbonyl amino where the arylgroup is substituted by C₁₋₆ alkyl or halogen),aryl-N—(C₁₋₆)alkylaminocarbonylamino where the aryl group is substitutedby C₁₋₆ alkyl or halogen), C₁₋₆ alkylaminocarbonyl-N—(C₁₋₆)alkyl amino,di(C₁₋₆)alkylaminocarbonyl-N—(C₁₋₆)alkyl amino,arylaminocarbonyl-N—(C₁₋₆)alkyl amino where the aryl group issubstituted by C₁₋₆ alkyl or halogen) andaryl-N—(C₁₋₆)alkylaminocarbonyl-N—(C₁₋₆)alkyl amino where the aryl groupis substituted by C₁₋₆ alkyl or halogen).

For substituted phenyl moieties, heterocyclyl and heteroaryl groups itis preferred that one or more substituents are independently selectedfrom halogen, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₁₋₆alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylthio, C₁₋₆ haloalkylthio, C₁₋₆alkylsulfinyl, C₁₋₆ haloalkylsulfinyl, C₁₋₆ alkylsulfonyl, C₁₋₆haloalkylsulfonyl, C₂₋₆ alkenyl, C₂₋₆ haloalkenyl, C₂₋₆ alkynyl, C₃₋₇cycloalkyl, nitro, cyano, CO₂H, C₁₋₆ alkylcarbonyl, C₁₋₆ alkoxycarbonyl,R²⁵R²⁶N or R²⁷R²⁸NC(O); wherein R²⁵, R²⁶, R²⁷ and R²⁸ are,independently, hydrogen or C₁₋₆ alkyl. Further preferred substituentsare aryl and heteroaryl groups.

Haloalkenyl groups are alkenyl groups which are substituted with one ormore of the same or different halogen atoms.

It is to be understood that dialkylamino substituents include thosewhere the dialkyl groups together with the N atom to which they areattached form a five, six or seven-membered heterocyclic ring which maycontain one or two further heteroatoms selected from O, N or S and whichis optionally substituted by one or two independently selected(C₁₋₆)alkyl groups. When heterocyclic rings are formed by joining twogroups on an N atom, the resulting rings are suitably pyrrolidine,piperidine, thiomorpholine and morpholine each of which may besubstituted by one or two independently selected (C₁₋₆) alkyl groups.

Preferably the optional substituents on an alkyl moiety include one ormore of halogen, nitro, cyano, HO₂C, C₁₋₁₀ alkoxy (itself optionallysubstituted by C₁₋₁₀ alkoxy), aryl(C₁₋₄)alkoxy, C₁₋₁₀ alkylthio, C₁₋₁₀alkylcarbonyl, C₁₋₁₀ alkoxycarbonyl, C₁₋₆ alkylaminocarbonyl, di(C₁₋₆alkyl)aminocarbonyl, (C₁₋₆)alkylcarbonyloxy, optionally substitutedphenyl, heteroaryl, aryloxy, arylcarbonyloxy, heteroaryloxy,heterocyclyl, heterocyclyloxy, C₃₋₇ cycloalkyl (itself optionallysubstituted with (C₁₋₆)alkyl or halogen), C₃₋₇ cycloalkyloxy, C₅₋₇cycloalkenyl, C₁₋₆ alkylsulfonyl, C₁₋₆ alkylsulfinyl,tri(C₁₋₄)alkylsilyl, tri(C₁₋₄)alkylsilyl(C₁₋₆)alkoxy,aryldi(C₁₋₄)alkylsilyl, (C₁₋₄)alkyldiarylsilyl and triarylsilyl.

Preferably the optional substituents on alkenyl or alkynyl include oneor more of halogen, aryl and C₃₋₇ cycloalkyl.

A preferred optional substituent for heterocyclyl is C₁₋₆ alkyl.

Preferably the optional substituents for cycloalkyl include halogen,cyano and C₁₋₃ alkyl.

Preferably the optional substituents for cycloalkenyl include C₁₋₃alkyl, halogen and cyano.

Preferred groups for T, Y, Ra, R¹, R², R⁴ and R⁸ in any combinationthereof are set out below.

Preferably Y is a single bond, C═O or C═S.

More preferably Y is a single bond or C═O.

Most preferably Y is C═O.

Preferably R¹ is hydrogen, C₁₋₆ alkyl, C₁₋₆ cyanoalkyl, C₁₋₆ haloalkyl,C₃₋₇ cycloalkyl(C₁₋₄)alkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl,heteroaryl(C₁₋₆)alkyl (wherein the heteroaryl group may be optionallysubstituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylsulfonyl, C₁₋₆ alkylsulfinyl, C₁₋₆alkylthio, C₁₋₆ alkoxycarbonyl, C₁₋₆ alkylcarbonylamino, arylcarbonyl,or two adjacent positions on the heteroaryl system may be cyclised toform a 5, 6 or 7 membered carbocyclic or heterocyclic ring, itselfoptionally substituted with halogen), aryl(C₁₋₆)alkyl (wherein the arylgroup may be optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl,C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylsulfonyl, C₁₋₆alkylsulfinyl, C₁₋₆ alkylthio, C₁₋₆ alkoxycarbonyl, C₁₋₆alkylcarbonylamino, arylcarbonyl, or two adjacent positions on the arylsystem may be cyclised to form a 5, 6 or 7 membered carbocyclic orheterocyclic ring, itself optionally substituted with halogen), C₁₋₆alkylcarbonylamino(C₁₋₆)alkyl, aryl (which may be optionally substitutedby halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆haloalkoxy, C₁₋₆ alkylsulfonyl, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylthio, C₁₋₆alkoxycarbonyl, C₁₋₆ alkylcarbonylamino, arylcarbonyl, or two adjacentpositions on the aryl system may be cyclised to form a 5, 6 or 7membered carbocyclic or heterocyclic ring, itself optionally substitutedwith halogen), heteroaryl (which may be optionally substituted by halo,nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy,C₁₋₆ alkylsulfonyl, C₁₋₆ alkylsulfinyl, C₁₋₆ alkylthio, C₁₋₆alkoxycarbonyl, C₁₋₆ alkylcarbonylamino, arylcarbonyl, or two adjacentpositions on the heteroaryl system may be cyclised to form a 5, 6 or 7membered carbocyclic or heterocyclic ring, itself optionally substitutedwith halogen), C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, phenoxy (wherein the phenylgroup is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy,C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino ordialkylamino), heteroaryloxy (optionally substituted by halo, nitro,cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆ haloalkoxy),heterocyclyloxy (optionally substituted by halo, C₁₋₆ alkyl, C₁₋₆haloalkyl, C₁₋₆ alkoxy or C₁₋₆ haloalkoxy), cyano, C₂₋₆ alkenyl, C₂₋₆alkynyl, C₃₋₆ cycloalkyl, C₅₋₇ cycloalkenyl, heterocyclyl (optionallysubstituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆alkoxy or C₁₋₆ haloalkoxy), C₁₋₆ alkylthio, C₁₋₆ haloalkylthio orNR¹³R¹⁴ where R¹³ and R¹⁴ are independently hydrogen, C₁₋₆ alkyl, C₁₋₆haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, phenyl (which may be optionallysubstituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, CN, NO₂, aryl, heteroaryl, amino, dialkylamino or C₁₋₄alkoxycarbonyl), phenyl (C₁₋₆)alkyl (wherein the phenyl group may beoptionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino,dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl, or two adjacentpositions on the phenyl ring may be cyclised to form a 5, 6 or 7membered carbocyclic or heterocyclic ring, itself optionally substitutedwith halogen), heteroaryl (C₁₋₆)alkyl (wherein the heteroaryl group maybe optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylsulfonyl, C₁₋₆alkylsulfinyl, C₁₋₆ alkylthio, C₁₋₆ alkoxycarbonyl, C₁₋₆alkylcarbonylamino, arylcarbonyl, or two adjacent positions on theheteroaryl system may be cyclised to form a 5, 6 or 7 memberedcarbocyclic or heterocyclic ring, itself optionally substituted withhalogen) or heteroaryl (which may be optionally substituted by halo,nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆haloalkoxy, C₁₋₄ alkoxycarbonyl C₁₋₆ alkylcarbonylamino,phenyloxycarbonylamino (wherein the phenyl group is optionallysubstituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino), amino,C₁₋₆ alkylamino or phenylamino (wherein the phenyl group is optionallysubstituted halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino)).

More preferably R¹ is C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆alkoxy(C₁₋₆)alkyl, heteroaryl(C₁₋₃)alkyl (wherein the heteroaryl groupmay be optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylsulfonyl, C₁₋₆alkoxycarbonyl, or two adjacent positions on the heteroaryl system maybe cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclicring, itself optionally substituted with halogen), phenyl(C₁₋₃)alkyl(wherein the phenyl group may be optionally substituted by halogen, C₁₋₄alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl,heteroaryl, amino, dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆alkoxycarbonyl, or two adjacent positions on the phenyl ring may becyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring,itself optionally substituted with halogen), phenyl (which may beoptionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino,dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl, or two adjacentpositions on the phenyl ring may be cyclised to form a 5, 6 or 7membered carbocyclic or heterocyclic ring, itself optionally substitutedwith halogen), heteroaryl (which may be optionally substituted by halo,nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy,C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl, or two adjacent positions onthe heteroaryl system may be cyclised to form a 5, 6 or 7 memberedcarbocyclic or heterocyclic ring, itself optionally substituted withhalogen), C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₂₋₆ alkenyl, heterocyclyl(optionally substituted by halo, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆alkoxy or C₁₋₆ haloalkoxy), C₁₋₆ alkylthio, C₁₋₆ haloalkylthio orNR¹³R¹⁴ where R¹³ and R¹⁴ are independently hydrogen, C₁₋₆ alkyl or C₁₋₆haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₂₋₆ alkylcarbonyl, phenylcarbonyl,(where the phenyl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl,amino or dialkylamino), phenyl(C₁₋₃)alkyl (wherein the phenyl group maybe optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino,dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl, or two adjacentpositions on the phenyl ring may be cyclised to form a 5, 6 or 7membered carbocyclic or heterocyclic ring, itself optionally substitutedwith halogen) or heteroaryl(C₁₋₃)alkyl (wherein the heteroaryl group maybe optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylsulfonyl, C₁₋₆alkylsulfinyl, C₁₋₆ alkylthio, C₁₋₆ alkoxycarbonyl, C₁₋₆alkylcarbonylamino, arylcarbonyl, or two adjacent positions on theheteroaryl system may be cyclised to form a 5, 6 or 7 memberedcarbocyclic or heterocyclic ring, itself optionally substituted withhalogen).

Even more preferably R¹ is C₁₋₆ alkyl, C₁₋₆ haloalkyl,heteroaryl(C₁₋₃)alkyl (wherein the heteroaryl group may be optionallysubstituted by halo, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl and where theheteroaryl group is a thiazole, pyridine, pyrimidine, pyrazine orpyridazine ring), heteroaryl (optionally substituted by halo, cyano,C₁₋₆ alkyl, C₁₋₆ haloalkyl and where the heteroaryl group is a pyridine,pyrimidine, 2,1,3-benzoxadiazole, pyrazine or pyridazine ring), C₁₋₆alkoxy, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₁₋₆ alkylamino, C₁₋₆alkyoxy(C₁₋₆)alkylamino or heteroaryl(C₁₋₃)alkylamino (wherein theheteroaryl group may be optionally substituted by halo, cyano, C₁₋₆alkyl, C₁₋₆ haloalkyl and where the heteroaryl group is a thiazole,pyridine, pyrimidine, pyrazine or pyridazine ring).

Most preferably R¹ is pyridyl (optionally substituted by halo, C₁₋₃alkyl or C₁₋₃ haloalkyl) especially halo-substituted pyridyl.

It is preferred that R² is hydrogen, hydroxy, C₁₋₆ alkyl or C₁₋₆haloalkyl.

More preferably R² is hydrogen, C₁₋₄ alkyl or C₁₋₄ haloalkyl.

Even more preferably R² is hydrogen or C₁₋₄ alkyl.

Yet more preferably R² is independently hydrogen or methyl.

Most preferably R² is hydrogen.

Preferably each R⁴ is independently halogen, cyano, C₁₋₈ alkyl, C₁₋₈haloalkyl, C₁₋₆ cyano alkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₃₋₇cycloalkyl(C₁₋₆)alkyl, C₅₋₆ cycloalkenyl(C₁₋₆)alkyl, C₃₋₆alkenyloxy(C₁₋₆)alkyl, C₃₋₆ alkynyloxy(C₁₋₆)alkyl, aryloxy(C₁₋₆)alkyl,C₁₋₆ carboxyalkyl, C₁₋₆ alkylcarbonyl(C₁₋₆)alkyl, C₂₋₆alkenylcarbonyl(C₁₋₆)alkyl, C₂₋₆ alkynylcarbonyl(C₁₋₆)-alkyl, C₁₋₆alkoxycarbonyl(C₁₋₆)alkyl, C₃₋₆ alkenyloxycarbonyl(C₁₋₆)alkyl, C₃₋₆alkynyloxycarbonyl(C₁₋₆)alkyl, aryloxycarbonyl(C₁₋₆)alkyl, C₁₋₆alkylthio(C₁₋₆)alkyl, C₁₋₆ alkylsulfinyl(C₁₋₆)alkyl, C₁₋₆alkylsulfonyl(C₁₋₆)alkyl, aminocarbonyl(C₁₋₆)alkyl, C₁₋₆alkylaminocarbonyl(C₁₋₆)alkyl, di(C₁₋₆)alkylaminocarbonyl(C₁₋₆)alkyl,phenyl(C₁₋₄)alkyl (wherein the phenyl group is optionally substituted byhalogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN,NO₂, aryl, heteroaryl, amino or dialkylamino), heteroaryl(C₁₋₄)alkyl(wherein the heteroaryl group is optionally substituted by halo, nitro,cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆ haloalkoxy),heterocyclyl(C₁₋₄)alkyl (wherein the heterocyclyl group is optionallysubstituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆alkoxy or C₁₋₆ haloalkoxy), C₂₋₆ alkenyl, aminocarbonyl(C₂₋₆)alkenyl,C₁₋₆ alkylaminocarbonyl(C₂₋₆)alkenyl,di(C₁₋₆)alkylaminocarbonyl(C₂₋₆)alkenyl, phenyl(C₂₋₄)-alkenyl, (whereinthe phenyl group is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl,amino or dialkylamino), C₂₋₆ alkynyl, trimethylsilyl(C₂₋₆)alkynyl,aminocarbonyl(C₂₋₆)alkynyl, C₁₋₆ alkylaminocarbonyl(C₂₋₆)alkynyl,di(C₁₋₆)alkylaminocarbonyl(C₂₋₆)alkynyl, C₁₋₆ alkoxycarbonyl, C₃₋₇cycloalkyl, C₃₋₇ halocycloalkyl, C₃₋₇ cyanocycloalkyl, C₁₋₃alkyl(C₃₋₇)-cycloalkyl, C₁₋₃ alkyl(C₃₋₇)halocycloalkyl, phenyl(optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino ordialkylamino), heteroaryl (optionally substituted by halo, nitro, cyano,C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆ haloalkoxy),heterocyclyl (wherein the heterocyclyl group is optionally substitutedby halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆haloalkoxy), or 2 adjacent groups R⁴ together with the carbon atoms towhich they are attached form a 4, 5, 6 or 7 membered carbocylic orheterocyclic ring which may be optionally substituted by halogen, C₁₋₈alkoxy, C₁₋₆ haloalkoxy, phenoxy (optionally substituted by halo, nitro,cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆ haloalkoxy),heteroaryloxy (optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl,C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆ haloalkoxy), C₁₋₈ alkylthio orR¹⁹R²⁰N where R¹⁹ and R²⁰ are, independently, hydrogen, C₁₋₈ alkyl, C₃₋₇cycloalkyl, C₃₋₆ alkenyl, C₃₋₆ alkynyl, C₃₋₆ haloalkyl, C₁₋₆alkoxycarbonyl or R¹⁹ and R²⁰ together with the N atom to which they areattached form a five, six or seven-membered heterocyclic ring which maycontain one or two further heteroatoms selected from O, N or S and whichmay be optionally substituted by one or two C₁₋₆ alkyl groups; n is 0,1, 2 or 3.

More preferably each R⁴ is independently halogen, cyano, C₁₋₈ alkyl,C₁₋₈ haloalkyl, C₁₋₈ cyanoalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₂₋₆ alkynyl,trimethylsilyl(C₂₋₆)alkynyl, C₁₋₆ alkoxycarbonyl, C₃₋₇ cycloalkyl, C₁₋₃alkyl (C₃₋₇) cycloalkyl, phenyl (optionally substituted by halogen, C₁₋₄alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl,heteroaryl, amino or dialkylamino), heterocyclyl (optionally substitutedby halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆haloalkoxy), C₁₋₈ alkoxy, C₁₋₆ haloalkoxy, phenoxy (optionallysubstituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino),heteroaryloxy (optionally substituted by halo, nitro, cyano, C₁₋₃ alkyl,C₁₋₃ haloalkyl, C₁₋₃ alkoxy or C₁₋₃ haloalkoxy), di(C₁₋₈)alkylamino, or2 adjacent groups R⁴ together with the carbon atoms to which they areattached form a 4, 5, 6 or 7 membered carbocylic or heterocyclic ringwhich may be optionally substituted by halogen; n is 0, 1, 2 or 3.

Even more preferably each R⁴ is independently halogen, cyano, C₁₋₈alkyl, C₁₋₈ haloalkyl, C₁₋₈ cyanoalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₂₋₆alkynyl, heterocyclyl (optionally substituted by C₁₋₆ alkyl), C₁₋₈alkoxy, C₁₋₆ haloalkoxy, phenoxy (optionally substituted by halo, cyano,C₁₋₃ alkyl or C₁₋₃ haloalkyl), heteroaryloxy (optionally substituted byhalo, cyano, C₁₋₃ alkyl or C₁₋₃ haloalkyl), di(C₁₋₈)alkylamino or 2adjacent groups R⁴ together with the carbon atoms to which they areattached form a 4, 5, 6 or 7 membered carbocylic or heterocyclic ringwhich may be optionally substituted by halogen; n is 0, 1, 2 or 3.

Yet more preferably each R⁴ is independently fluoro, chloro, bromo,cyano, C₁₋₄ alkyl, C₁₋₄ haloalkyl, C₁₋₄ cyanoalkyl or C₁₋₃alkoxy(C₁₋₃)alkyl; n is 0, 1, 2 or 3, preferably 0, 1 or 2.

Most preferably each R⁴ is independently fluoro, chloro, bromo, C₁₋₄alkyl or C₁₋₄ haloalkyl; n is 1, 2 or 3, preferably 1 or 2.

Preferably R⁸ is C₁₋₁₀ alkyl, C₁₋₁₀ haloalkyl, aryl(C₁₋₆)alkyl (whereinthe aryl group is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl,amino or dialkylamino), heteroaryl(C₁₋₆)alkyl (wherein the heteroarylgroup is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy,C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino ordialkylamino), arylcarbonyl-(C₁₋₆)alkyl (wherein the aryl group may beoptionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino ordialkylamino and the alkyl group may be optionally substituted by aryl),C₂₋₈ alkenyl, C₂₋₈ haloalkenyl, aryl(C₂₋₄-alkenyl (wherein the arylgroup is optionally substituted halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino ordialkylamino, C₁₋₆ alkoxycarbonyl, or two adjacent substituents cancyclise to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring),heteroaryl(C₂₋₄-alkenyl (wherein the heteroaryl group is optionallysubstituted halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino, C₁₋₆alkoxycarbonyl, or two adjacent substituents can cyclise to form a 5, 6or 7 membered carbocyclic or heterocyclic ring), C₂₋₆ alkynyl,phenyl(C₂₋₆)alkynyl (wherein the phenyl group is optionally substitutedby halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy,CN, NO₂, aryl, heteroaryl, amino or dialkylamino), C₃₋₇ cycloalkyl, C₁₋₆alkoxycarbonyl, C₁₋₆ alkylcarbonyl, C₁₋₆ haloalkylcarbonyl oraryl(C₂₋₆)alkenylcarbonyl (wherein the aryl group may be optionallysubstituted halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino), or—C(R⁵¹)(R⁵²)—[CR⁵³═CR⁵⁴]z-R⁵⁵ where z is 1 or 2, R⁵¹ and R⁵² are eachindependently H, halo or C₁₋₂ alkyl, R⁵³ and R⁵⁴ are each independentlyH, halogen, C₁₋₄ alkyl or C₁₋₄ haloalkyl and R⁵⁵ is optionallysubstituted aryl or optionally substituted heteroaryl.

More preferably R⁸ is phenyl(C₁₋₄)alkyl (wherein the phenyl group isoptionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino ordialkylamino), heteroaryl(C₁₋₆)alkyl (wherein the heteroaryl group isoptionally substituted halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl,C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino),phenyl(C₂₋₆)alkenyl (wherein the phenyl group is optionally substitutedby halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy,CN, NO₂, aryl, heteroaryl, amino or dialkylamino),heteroaryl(C₂₋₆)alkenyl (wherein the heteroaryl group is optionallysubstituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino) orphenyl(C₂₋₆)alkynyl (wherein the phenyl group is optionally substitutedby halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy,CN, NO₂, aryl, heteroaryl, amino or dialkylamino, or—C(R⁵¹)(R⁵²)—[CR⁵³═CR⁵⁴]z-R⁵⁵ where z is 1 or 2, R⁵¹ and R⁵² are eachindependently H, halo or C₁₋₂ alkyl, R⁵³ and R⁵⁴ are each independentlyH, halogen, C₁₋₄ alkyl or C₁₋₄ haloalkyl and R⁵⁵ is optionallysubstituted aryl or optionally substituted heteroaryl.

Most preferably R⁸ is —C(R⁵¹)(R⁵²)—[CR⁵³═CR⁵⁴]z-R⁵⁵ where z is 1 or 2,preferably 1, R⁵¹ and R⁵² are each independently H or C₁₋₂ alkyl, R⁵³and R⁵⁴ are each independently H, halogen, C₁₋₄ alkyl or C₁₋₄ haloalkyland R⁵⁵ is phenyl substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino ordialkylamino or heteroaryl substituted by halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl,amino or dialkylamino.

R⁵¹ and R⁵² are preferably hydrogen.

R⁵³ and R⁵⁴ are preferably hydrogen or halogen, especially hydrogen.

R⁵⁵ is preferably phenyl substituted with one to three substituentsselected from halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino.

Preferably each Ra is independently halo, cyano, C₁₋₃ alkyl, hydroxy ortwo Ra groups together with the carbon atom to which they are attachedform ═O, ═S, ═NRb, ═CRcRd where Rb, Rc and Rd are independently H oroptionally substituted alkyl, and p is 0, 1 or 2.

More preferably each Ra is independently fluoro, methyl, hydroxy or twoRa groups together with the carbon atom to which they are attached forma carbonyl group and p is 0, 1 or 2.

Most preferably p is 0.

It is preferred that that ring

is a 6-membered aromatic ring or is 5 or 6 membered heteroaromatic ringwherein the ring members are each independently CH, S, N, NR⁴, O, or CR⁴provided that at least one ring member is other than CH or CR⁴ and thatthere are no more than one O or S atoms present in the ring.

More preferably the ring

is a benzene, pyridine, pyrimidine, pyrazine, pyridazine, triazine,furan, thiophene, pyrrole, imidazole, pyrazole, oxazole, thiazole,isoxazole, isothiazole, [1,2,3]triazole, [1,2,3]oxadiazole or[1,2,3]thiadiazole.

Most preferably the ring

is a benzene or pyridine ring.

Certain compounds of formula (I) are novel and as such form a furtheraspect of the invention. One group of novel compounds are compounds offormula I′

wherein R¹, R², R⁴, Ra, T, Y, n and p are as defined in relation toformula I and R⁸ is —C(R⁵¹)(R⁵²)—[CR⁵³═CR⁵⁴]z-R⁵⁵ where z is 1 or 2,preferably 1, R⁵¹ and R⁵² are each independently H or C₁₋₂ alkyl, R⁵³and R⁵⁴ are each independently H, halogen, C₁₋₄ alkyl or C₁₋₄ haloalkyland R⁵⁵ is phenyl substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino ordialkylamino or heteroaryl substituted by halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl,amino or dialkylamino.

The compounds in Tables I to XXV below illustrate the compounds of theinvention.

Table I provides 897 compounds of formula Ia

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

TABLE 1 Compound No R⁸ R^(4a) R^(4b) R^(4c) R^(4d) I-1 4-chlorobenzyl HH H H I-2 Cinnamyl H H H H I-3 4-chlorocinnamyl H H H H I-44-fluorocinnamyl H H H H I-5 4-bromocinnamyl H H H H I-64-trifluoromethylcinnamyl H H H H I-7 4-trifluoromethoxycinnamyl H H H HI-8 4-pentafluoroethoxycinnamyl H H H H I-9 4-methoxycinnamyl H H H HI-10 4-ethoxycinnamyl H H H H I-11 4-cyanocinnamyl H H H H I-123-(6-chloro-pyridin-3-yl)-allyl H H H H I-133-(4-chlorophenyl)-but-2-enyl H H H H I-14 3-(4-chlorophenyl)-3-fluoro-H H H H allyl I-15 3-chloro-4-fluoro-cinnamyl H H H H I-163,5-dichloro-cinnamyl H H H H I-17 5-phenyl-penta-2,4-dienyl H H H HI-18 4-isopropyloxycarbonylamino- H H H H cinnamyl I-193-naphthalen-2-yl-allyl H H H H I-20 3-(5-trifluoromethyl-pyridin-2- H HH H yl)-allyl I-21 3-(5-chloro-pyridin-2-yl)-allyl H H H H I-223-pyridin-4-yl-allyl H H H H I-23 3-(2-Chloro-pyridin-4-yl)-allyl H H HH I-24 4-chlorobenzyl H F H H I-25 Cinnamyl H F H H I-264-chlorocinnamyl H F H H I-27 4-fluorocinnamyl H F H H I-284-bromocinnamyl H F H H I-29 4-trifluoromethylcinnamyl H F H H I-304-trifluoromethoxycinnamyl H F H H I-31 4-pentafluoroethoxycinnamyl H FH H I-32 4-methoxycinnamyl H F H H I-33 4-ethoxycinnamyl H F H H I-344-cyanocinnamyl H F H H I-35 3-(6-chloro-pyridin-3-yl)-allyl H F H HI-36 3-(4-chlorophenyl)-but-2-enyl H F H H I-373-(4-chlorophenyl)-3-fluoro- H F H H allyl I-383-chloro-4-fluoro-cinnamyl H F H H I-39 3,5-dichloro-cinnamyl H F H HI-40 5-phenyl-penta-2,4-dienyl H F H H I-41 4-isopropyloxycarbonylamino-H F H H cinnamyl I-42 3-naphthalen-2-yl-allyl H F H H I-433-(5-trifluoromethyl-pyridin-2- H F H H yl)-allyl I-443-(5-chloro-pyridin-2-yl)-allyl H F H H I-45 3-pyridin-4-yl-allyl H F HH I-46 3-(2-Chloro-pyridin-4-yl)-allyl H F H H I-47 4-chlorobenzyl H ClH H I-48 Cinnamyl H Cl H H I-49 4-chlorocinnamyl H Cl H H I-504-fluorocinnamyl H Cl H H I-51 4-bromocinnamyl H Cl H H I-524-trifluoromethylcinnamyl H Cl H H I-53 4-trifluoromethoxycinnamyl H ClH H I-54 4-pentafluoroethoxycinnamyl H Cl H H I-55 4-methoxycinnamyl HCl H H I-56 4-ethoxycinnamyl H Cl H H I-57 4-cyanocinnamyl H Cl H H I-583-(6-chloro-pyridin-3-yl)-allyl H Cl H H I-593-(4-chlorophenyl)-but-2-enyl H Cl H H I-60 3-(4-chlorophenyl)-3-fluoro-H Cl H H allyl I-61 3-chloro-4-fluoro-cinnamyl H Cl H H I-623,5-dichloro-cinnamyl H Cl H H I-63 5-phenyl-penta-2,4-dienyl H Cl H HI-64 4-isopropyloxycarbonylamino- H Cl H H cinnamyl I-653-naphthalen-2-yl-allyl H Cl H H I-66 3-(5-trifluoromethyl-pyridin-2- HCl H H yl)-allyl I-67 3-(5-chloro-pyridin-2-yl)-allyl H Cl H H I-683-pyridin-4-yl-allyl H Cl H H I-69 3-(2-Chloro-pyridin-4-yl)-allyl H ClH H I-70 4-chlorobenzyl H H F H I-71 Cinnamyl H H F H I-724-chlorocinnamyl H H F H I-73 4-fluorocinnamyl H H F H I-744-bromocinnamyl H H F H I-75 4-trifluoromethylcinnamyl H H F H I-764-trifluoromethoxycinnamyl H H F H I-77 4-pentafluoroethoxycinnamyl H HF H I-78 4-methoxycinnamyl H H F H I-79 4-ethoxycinnamyl H H F H I-804-cyanocinnamyl H H F H I-81 3-(6-chloro-pyridin-3-yl)-allyl H H F HI-82 3-(4-chlorophenyl)-but-2-enyl H H F H I-833-(4-chlorophenyl)-3-fluoro- H H F H allyl I-843-chloro-4-fluoro-cinnamyl H H F H I-85 3,5-dichloro-cinnamyl H H F HI-86 5-phenyl-penta-2,4-dienyl H H F H I-87 4-isopropyloxycarbonylamino-H H F H cinnamyl I-88 3-naphthalen-2-yl-allyl H H F H I-893-(5-trifluoromethyl-pyridin-2- H H F H yl)-allyl I-903-(5-chloro-pyridin-2-yl)-allyl H H F H I-91 3-pyridin-4-yl-allyl H H FH I-92 3-(2-Chloro-pyridin-4-yl)-allyl H H F H I-93 4-chlorobenzyl H HCl H I-94 Cinnamyl H H Cl H I-95 4-chlorocinnamyl H H Cl H I-964-fluorocinnamyl H H Cl H I-97 4-bromocinnamyl H H Cl H I-984-trifluoromethylcinnamyl H H Cl H I-99 4-trifluoromethoxycinnamyl H HCl H I-100 4-pentafluoroethoxycinnamyl H H Cl H I-101 4-methoxycinnamylH H Cl H I-102 4-ethoxycinnamyl H H Cl H I-103 4-cyanocinnamyl H H Cl HI-104 3-(6-chloro-pyridin-3-yl)-allyl H H Cl H I-1053-(4-chlorophenyl)-but-2-enyl H H Cl H I-1063-(4-chlorophenyl)-3-fluoro- H H Cl H allyl I-1073-chloro-4-fluoro-cinnamyl H H Cl H I-108 3,5-dichloro-cinnamyl H H Cl HI-109 5-phenyl-penta-2,4-dienyl H H Cl H I-1104-isopropyloxycarbonylamino- H H Cl H cinnamyl I-1113-naphthalen-2-yl-allyl H H Cl H I-112 3-(5-trifluoromethyl-pyridin-2- HH Cl H yl)-allyl I-113 3-(5-chloro-pyridin-2-yl)-allyl H H Cl H I-1143-pyridin-4-yl-allyl H H Cl H I-115 3-(2-Chloro-pyridin-4-yl)-allyl H HCl H I-116 4-chlorobenzyl Cl Cl H H I-117 Cinnamyl Cl Cl H H I-1184-chlorocinnamyl Cl Cl H H I-119 4-fluorocinnamyl Cl Cl H H I-1204-bromocinnamyl Cl Cl H H I-121 4-trifluoromethylcinnamyl Cl Cl H HI-122 4-trifluoromethoxycinnamyl Cl Cl H H I-1234-pentafluoroethoxycinnamyl Cl Cl H H I-124 4-methoxycinnamyl Cl Cl H HI-125 4-ethoxycinnamyl Cl Cl H H I-126 4-cyanocinnamyl Cl Cl H H I-1273-(6-chloro-pyridin-3-yl)-allyl Cl Cl H H I-1283-(4-chlorophenyl)-but-2-enyl Cl Cl H H I-1293-(4-chlorophenyl)-3-fluoro- Cl Cl H H allyl I-1303-chloro-4-fluoro-cinnamyl Cl Cl H H I-131 3,5-dichloro-cinnamyl Cl Cl HH I-132 5-phenyl-penta-2,4-dienyl Cl Cl H H I-1334-isopropyloxycarbonylamino- Cl Cl H H cinnamyl I-1343-naphthalen-2-yl-allyl Cl Cl H H I-135 3-(5-trifluoromethyl-pyridin-2-Cl Cl H H yl)-allyl I-136 3-(5-chloro-pyridin-2-yl)-allyl Cl Cl H HI-137 3-pyridin-4-yl-allyl Cl Cl H H I-1383-(2-Chloro-pyridin-4-yl)-allyl Cl Cl H H I-139 4-chlorobenzyl F F H HI-140 Cinnamyl F F H H I-141 4-chlorocinnamyl F F H H I-1424-fluorocinnamyl F F H H I-143 4-bromocinnamyl F F H H I-1444-trifluoromethylcinnamyl F F H H I-145 4-trifluoromethoxycinnamyl F F HH I-146 4-pentafluoroethoxycinnamyl F F H H I-147 4-methoxycinnamyl F FH H I-148 4-ethoxycinnamyl F F H H I-149 4-cyanocinnamyl F F H H I-1503-(6-chloro-pyridin-3-yl)-allyl F F H H I-1513-(4-chlorophenyl)-but-2-enyl F F H H I-152 3-(4-chlorophenyl)-3-fluoro-F F H H allyl I-153 3-chloro-4-fluoro-cinnamyl F F H H I-1543,5-dichloro-cinnamyl F F H H I-155 5-phenyl-penta-2,4-dienyl F F H HI-156 4-isopropyloxycarbonylamino- F F H H cinnamyl I-1573-naphthalen-2-yl-allyl F F H H I-158 3-(5-trifluoromethyl-pyridin-2- FF H H yl)-allyl I-159 3-(5-chloro-pyridin-2-yl)-allyl F F H H I-1603-pyridin-4-yl-allyl F F H H I-161 3-(2-Chloro-pyridin-4-yl)-allyl F F HH I-162 4-chlorobenzyl F H F H I-163 Cinnamyl F H F H I-1644-chlorocinnamyl F H F H I-165 4-fluorocinnamyl F H F H I-1664-bromocinnamyl F H F H I-167 4-trifluoromethylcinnamyl F H F H I-1684-trifluoromethoxycinnamyl F H F H I-169 4-pentafluoroethoxycinnamyl F HF H I-170 4-methoxycinnamyl F H F H I-171 4-ethoxycinnamyl F H F H I-1724-cyanocinnamyl F H F H I-173 3-(6-chloro-pyridin-3-yl)-allyl F H F HI-174 3-(4-chlorophenyl)-but-2-enyl F H F H I-1753-(4-chlorophenyl)-3-fluoro- F H F H allyl I-1763-chloro-4-fluoro-cinnamyl F H F H I-177 3,5-dichloro-cinnamyl F H F HI-178 5-phenyl-penta-2,4-dienyl F H F H I-1794-isopropyloxycarbonylamino- F H F H cinnamyl I-1803-naphthalen-2-yl-allyl F H F H I-181 3-(5-trifluoromethyl-pyridin-2- FH F H yl)-allyl I-182 3-(5-chloro-pyridin-2-yl)-allyl F H F H I-1833-pyridin-4-yl-allyl F H F H I-184 3-(2-Chloro-pyridin-4-yl)-allyl F H FH I-185 4-chlorobenzyl F H H F I-186 Cinnamyl F H H F I-1874-chlorocinnamyl F H H F I-188 4-fluorocinnamyl F H H F I-1894-bromocinnamyl F H H F I-190 4-trifluoromethylcinnamyl F H H F I-1914-trifluoromethoxycinnamyl F H H F I-192 4-pentafluoroethoxycinnamyl F HH F I-193 4-methoxycinnamyl F H H F I-194 4-ethoxycinnamyl F H H F I-1954-cyanocinnamyl F H H F I-196 3-(6-chloro-pyridin-3-yl)-allyl F H H FI-197 3-(4-chlorophenyl)-but-2-enyl F H H F I-1983-(4-chlorophenyl)-3-fluoro- F H H F allyl I-1993-chloro-4-fluoro-cinnamyl F H H F I-200 3,5-dichloro-cinnamyl F H H FI-201 5-phenyl-penta-2,4-dienyl F H H F I-2024-isopropyloxycarbonylamino- F H H F cinnamyl I-2033-naphthalen-2-yl-allyl F H H F I-204 3-(5-trifluoromethyl-pyridin-2- FH H F yl)-allyl I-205 3-(5-chloro-pyridin-2-yl)-allyl F H H F I-2063-pyridin-4-yl-allyl F H H F I-207 3-(2-Chloro-pyridin-4-yl)-allyl F H HF I-208 4-chlorobenzyl Cl H Cl H I-209 Cinnamyl Cl H Cl H I-2104-chlorocinnamyl Cl H Cl H I-211 4-fluorocinnamyl Cl H Cl H I-2124-bromocinnamyl Cl H Cl H I-213 4-trifluoromethylcinnamyl Cl H Cl HI-214 4-trifluoromethoxycinnamyl Cl H Cl H I-2154-pentafluoroethoxycinnamyl Cl H Cl H I-216 4-methoxycinnamyl Cl H Cl HI-217 4-ethoxycinnamyl Cl H Cl H I-218 4-cyanocinnamyl Cl H Cl H I-2193-(6-chloro-pyridin-3-yl)-allyl Cl H Cl H I-2203-(4-chlorophenyl)-but-2-enyl Cl H Cl H I-2213-(4-chlorophenyl)-3-fluoro- Cl H Cl H allyl I-2223-chloro-4-fluoro-cinnamyl Cl H Cl H I-223 3,5-dichloro-cinnamyl Cl H ClH I-224 5-phenyl-penta-2,4-dienyl Cl H Cl H I-2254-isopropyloxycarbonylamino- Cl H Cl H cinnamyl I-2263-naphthalen-2-yl-allyl Cl H Cl H I-227 3-(5-trifluoromethyl-pyridin-2-Cl H Cl H yl)-allyl I-228 3-(5-chloro-pyridin-2-yl)-allyl Cl H Cl HI-229 3-pyridin-4-yl-allyl Cl H Cl H I-2303-(2-Chloro-pyridin-4-yl)-allyl Cl H Cl H I-231 4-chlorobenzyl Cl H H ClI-232 Cinnamyl Cl H H Cl I-233 4-chlorocinnamyl Cl H H Cl I-2344-fluorocinnamyl Cl H H Cl I-235 4-bromocinnamyl Cl H H Cl I-2364-trifluoromethylcinnamyl Cl H H Cl I-237 4-trifluoromethoxycinnamyl ClH H Cl I-238 4-pentafluoroethoxycinnamyl Cl H H Cl I-2394-methoxycinnamyl Cl H H Cl I-240 4-ethoxycinnamyl Cl H H Cl I-2414-cyanocinnamyl Cl H H Cl I-242 3-(6-chloro-pyridin-3-yl)-allyl Cl H HCl I-243 3-(4-chlorophenyl)-but-2-enyl Cl H H Cl I-2443-(4-chlorophenyl)-3-fluoro- Cl H H Cl allyl I-2453-chloro-4-fluoro-cinnamyl Cl H H Cl I-246 3,5-dichloro-cinnamyl Cl H HCl I-247 5-phenyl-penta-2,4-dienyl Cl H H Cl I-2484-isopropyloxycarbonylamino- Cl H H Cl cinnamyl I-2493-naphthalen-2-yl-allyl Cl H H Cl I-250 3-(5-trifluoromethyl-pyridin-2-Cl H H Cl yl)-allyl I-251 3-(5-chloro-pyridin-2-yl)-allyl Cl H H ClI-252 3-pyridin-4-yl-allyl Cl H H Cl I-2533-(2-Chloro-pyridin-4-yl)-allyl Cl H H Cl I-254 4-chlorobenzyl F Cl H HI-255 Cinnamyl F Cl H H I-256 4-chlorocinnamyl F Cl H H I-2574-fluorocinnamyl F Cl H H I-258 4-bromocinnamyl F Cl H H I-2594-trifluoromethylcinnamyl F Cl H H I-260 4-trifluoromethoxycinnamyl F ClH H I-261 4-pentafluoroethoxycinnamyl F Cl H H I-262 4-methoxycinnamyl FCl H H I-263 4-ethoxycinnamyl F Cl H H I-264 4-cyanocinnamyl F Cl H HI-265 3-(6-chloro-pyridin-3-yl)-allyl F Cl H H I-2663-(4-chlorophenyl)-but-2-enyl F Cl H H I-2673-(4-chlorophenyl)-3-fluoro- F Cl H H allyl I-2683-chloro-4-fluoro-cinnamyl F Cl H H I-269 3,5-dichloro-cinnamyl F Cl H HI-270 5-phenyl-penta-2,4-dienyl F Cl H H I-2714-isopropyloxycarbonylamino- F Cl H H cinnamyl I-2723-naphthalen-2-yl-allyl F Cl H H I-273 3-(5-trifluoromethyl-pyridin-2- FCl H H yl)-allyl I-274 3-(5-chloro-pyridin-2-yl)-allyl F Cl H H I-2753-pyridin-4-yl-allyl F Cl H H I-276 3-(2-Chloro-pyridin-4-yl)-allyl F ClH H I-277 4-chlorobenzyl F H Cl H I-278 Cinnamyl F H Cl H I-2794-chlorocinnamyl F H Cl H I-280 4-fluorocinnamyl F H Cl H I-2814-bromocinnamyl F H Cl H I-282 4-trifluoromethylcinnamyl F H Cl H I-2834-trifluoromethoxycinnamyl F H Cl H I-284 4-pentafluoroethoxycinnamyl FH Cl H I-285 4-methoxycinnamyl F H Cl H I-286 4-ethoxycinnamyl F H Cl HI-287 4-cyanocinnamyl F H Cl H I-288 3-(6-chloro-pyridin-3-yl)-allyl F HCl H I-289 3-(4-chlorophenyl)-but-2-enyl F H Cl H I-2903-(4-chlorophenyl)-3-fluoro- F H Cl H allyl I-2913-chloro-4-fluoro-cinnamyl F H Cl H I-292 3,5-dichloro-cinnamyl F H Cl HI-293 5-phenyl-penta-2,4-dienyl F H Cl H I-2944-isopropyloxycarbonylamino- F H Cl H cinnamyl I-2953-naphthalen-2-yl-allyl F H Cl H I-296 3-(5-trifluoromethyl-pyridin-2- FH Cl H yl)-allyl I-297 3-(5-chloro-pyridin-2-yl)-allyl F H Cl H I-2983-pyridin-4-yl-allyl F H Cl H I-299 3-(2-Chloro-pyridin-4-yl)-allyl F HCl H I-300 4-chlorobenzyl F H H Cl I-301 Cinnamyl F H H Cl I-3024-chlorocinnamyl F H H Cl I-303 4-fluorocinnamyl F H H Cl I-3044-bromocinnamyl F H H Cl I-305 4-trifluoromethylcinnamyl F H H Cl I-3064-trifluoromethoxycinnamyl F H H Cl I-307 4-pentafluoroethoxycinnamyl FH H Cl I-308 4-methoxycinnamyl F H H Cl I-309 4-ethoxycinnamyl F H H ClI-310 4-cyanocinnamyl F H H Cl I-311 3-(6-chloro-pyridin-3-yl)-allyl F HH Cl I-312 3-(4-chlorophenyl)-but-2-enyl F H H Cl I-3133-(4-chlorophenyl)-3-fluoro- F H H Cl allyl I-3143-chloro-4-fluoro-cinnamyl F H H Cl I-315 3,5-dichloro-cinnamyl F H H ClI-316 5-phenyl-penta-2,4-dienyl F H H Cl I-3174-isopropyloxycarbonylamino- F H H Cl cinnamyl I-3183-naphthalen-2-yl-allyl F H H Cl I-319 3-(5-trifluoromethyl-pyridin-2- FH H Cl yl)-allyl I-320 3-(5-chloro-pyridin-2-yl)-allyl F H H Cl I-3213-pyridin-4-yl-allyl F H H Cl I-322 3-(2-Chloro-pyridin-4-yl)-allyl F HH Cl I-323 4-chlorobenzyl Cl F H H I-324 Cinnamyl Cl F H H I-3254-chlorocinnamyl Cl F H H I-326 4-fluorocinnamyl Cl F H H I-3274-bromocinnamyl Cl F H H I-328 4-trifluoromethylcinnamyl Cl F H H I-3294-trifluoromethoxycinnamyl Cl F H H I-330 4-pentafluoroethoxycinnamyl ClF H H I-331 4-methoxycinnamyl Cl F H H I-332 4-ethoxycinnamyl Cl F H HI-333 4-cyanocinnamyl Cl F H H I-334 3-(6-chloro-pyridin-3-yl)-allyl ClF H H I-335 3-(4-chlorophenyl)-but-2-enyl Cl F H H I-3363-(4-chlorophenyl)-3-fluoro- Cl F H H allyl I-3373-chloro-4-fluoro-cinnamyl Cl F H H I-338 3,5-dichloro-cinnamyl Cl F H HI-339 5-phenyl-penta-2,4-dienyl Cl F H H I-3404-isopropyloxycarbonylamino- Cl F H H cinnamyl I-3413-naphthalen-2-yl-allyl Cl F H H I-342 3-(5-trifluoromethyl-pyridin-2-Cl F H H yl)-allyl I-343 3-(5-chloro-pyridin-2-yl)-allyl Cl F H H I-3443-pyridin-4-yl-allyl Cl F H H I-345 3-(2-Chloro-pyridin-4-yl)-allyl Cl FH H I-346 4-chlorobenzyl H F Cl H I-347 Cinnamyl H F Cl H I-3484-chlorocinnamyl H F Cl H I-349 4-fluorocinnamyl H F Cl H I-3504-bromocinnamyl H F Cl H I-351 4-trifluoromethylcinnamyl H F Cl H I-3524-trifluoromethoxycinnamyl H F Cl H I-353 4-pentafluoroethoxycinnamyl HF Cl H I-354 4-methoxycinnamyl H F Cl H I-355 4-ethoxycinnamyl H F Cl HI-356 4-cyanocinnamyl H F Cl H I-357 3-(6-chloro-pyridin-3-yl)-allyl H FCl H I-358 3-(4-chlorophenyl)-but-2-enyl H F Cl H I-3593-(4-chlorophenyl)-3-fluoro- H F Cl H allyl I-3603-chloro-4-fluoro-cinnamyl H F Cl H I-361 3,5-dichloro-cinnamyl H F Cl HI-362 5-phenyl-penta-2,4-dienyl H F Cl H I-3634-isopropyloxycarbonylamino- H F Cl H cinnamyl I-3643-naphthalen-2-yl-allyl H F Cl H I-365 3-(5-trifluoromethyl-pyridin-2- HF Cl H yl)-allyl I-366 3-(5-chloro-pyridin-2-yl)-allyl H F Cl H I-3673-pyridin-4-yl-allyl H F Cl H I-368 3-(2-Chloro-pyridin-4-yl)-allyl H FCl H I-369 4-chlorobenzyl H F H Cl I-370 Cinnamyl H F H Cl I-3714-chlorocinnamyl H F H Cl I-372 4-fluorocinnamyl H F H Cl I-3734-bromocinnamyl H F H Cl I-374 4-trifluoromethylcinnamyl H F H Cl I-3754-trifluoromethoxycinnamyl H F H Cl I-376 4-pentafluoroethoxycinnamyl HF H Cl I-377 4-methoxycinnamyl H F H Cl I-378 4-ethoxycinnamyl H F H ClI-379 4-cyanocinnamyl H F H Cl I-380 3-(6-chloro-pyridin-3-yl)-allyl H FH Cl I-381 3-(4-chlorophenyl)-but-2-enyl H F H Cl I-3823-(4-chlorophenyl)-3-fluoro- H F H Cl allyl I-3833-chloro-4-fluoro-cinnamyl H F H Cl I-384 3,5-dichloro-cinnamyl H F H ClI-385 5-phenyl-penta-2,4-dienyl H F H Cl I-3864-isopropyloxycarbonylamino- H F H Cl cinnamyl I-3873-naphthalen-2-yl-allyl H F H Cl I-388 3-(5-trifluoromethyl-pyridin-2- HF H Cl yl)-allyl I-389 3-(5-chloro-pyridin-2-yl)-allyl H F H Cl I-3903-pyridin-4-yl-allyl H F H Cl I-391 3-(2-Chloro-pyridin-4-yl)-allyl H FH Cl I-392 4-chlorobenzyl Cl H F H I-393 Cinnamyl Cl H F H I-3944-chlorocinnamyl Cl H F H I-395 4-fluorocinnamyl Cl H F H I-3964-bromocinnamyl Cl H F H I-397 4-trifluoromethylcinnamyl Cl H F H I-3984-trifluoromethoxycinnamyl Cl H F H I-399 4-pentafluoroethoxycinnamyl ClH F H I-400 4-methoxycinnamyl Cl H F H I-401 4-ethoxycinnamyl Cl H F HI-402 4-cyanocinnamyl Cl H F H I-403 3-(6-chloro-pyridin-3-yl)-allyl ClH F H I-404 3-(4-chlorophenyl)-but-2-enyl Cl H F H I-4053-(4-chlorophenyl)-3-fluoro- Cl H F H allyl I-4063-chloro-4-fluoro-cinnamyl Cl H F H I-407 3,5-dichloro-cinnamyl Cl H F HI-408 5-phenyl-penta-2,4-dienyl Cl H F H I-4094-isopropyloxycarbonylamino- Cl H F H cinnamyl I-4103-naphthalen-2-yl-allyl Cl H F H I-411 3-(5-trifluoromethyl-pyridin-2-Cl H F H yl)-allyl I-412 3-(5-chloro-pyridin-2-yl)-allyl Cl H F H I-4133-pyridin-4-yl-allyl Cl H F H I-414 3-(2-Chloro-pyridin-4-yl)-allyl Cl HF H I-415 4-chlorobenzyl H Cl F H I-416 Cinnamyl H Cl F H I-4174-chlorocinnamyl H Cl F H I-418 4-fluorocinnamyl H Cl F H I-4194-bromocinnamyl H Cl F H I-420 4-trifluoromethylcinnamyl H Cl F H I-4214-trifluoromethoxycinnamyl H Cl F H I-422 4-pentafluoroethoxycinnamyl HCl F H I-423 4-methoxycinnamyl H Cl F H I-424 4-ethoxycinnamyl H Cl F HI-425 4-cyanocinnamyl H Cl F H I-426 3-(6-chloro-pyridin-3-yl)-allyl HCl F H I-427 3-(4-chlorophenyl)-but-2-enyl H Cl F H I-4283-(4-chlorophenyl)-3-fluoro- H Cl F H allyl I-4293-chloro-4-fluoro-cinnamyl H Cl F H I-430 3,5-dichloro-cinnamyl H Cl F HI-431 5-phenyl-penta-2,4-dienyl H Cl F H I-4324-isopropyloxycarbonylamino- H Cl F H cinnamyl I-4333-naphthalen-2-yl-allyl H Cl F H I-434 3-(5-trifluoromethyl-pyridin-2- HCl F H yl)-allyl I-435 3-(5-chloro-pyridin-2-yl)-allyl H Cl F H I-4363-pyridin-4-yl-allyl H Cl F H I-437 3-(2-Chloro-pyridin-4-yl)-allyl H ClF H I-438 4-chlorobenzyl H H F Cl I-439 Cinnamyl H H F Cl I-4404-chlorocinnamyl H H F Cl I-441 4-fluorocinnamyl H H F Cl I-4424-bromocinnamyl H H F Cl I-443 4-trifluoromethylcinnamyl H H F Cl I-4444-trifluoromethoxycinnamyl H H F Cl I-445 4-pentafluoroethoxycinnamyl HH F Cl I-446 4-methoxycinnamyl H H F Cl I-447 4-ethoxycinnamyl H H F ClI-448 4-cyanocinnamyl H H F Cl I-449 3-(6-chloro-pyridin-3-yl)-allyl H HF Cl I-450 3-(4-chlorophenyl)-but-2-enyl H H F Cl I-4513-(4-chlorophenyl)-3-fluoro- H H F Cl allyl I-4523-chloro-4-fluoro-cinnamyl H H F Cl I-453 3,5-dichloro-cinnamyl H H F ClI-454 5-phenyl-penta-2,4-dienyl H H F Cl I-4554-isopropyloxycarbonylamino- H H F Cl cinnamyl I-4563-naphthalen-2-yl-allyl H H F Cl I-457 3-(5-trifluoromethyl-pyridin-2- HH F Cl yl)-allyl I-458 3-(5-chloro-pyridin-2-yl)-allyl H H F Cl I-4593-pyridin-4-yl-allyl H H F Cl I-460 3-(2-Chloro-pyridin-4-yl)-allyl H HF Cl I-461 4-chlorobenzyl Cl H H F I-462 Cinnamyl Cl H H F I-4634-chlorocinnamyl Cl H H F I-464 4-fluorocinnamyl Cl H H F I-4654-bromocinnamyl Cl H H F I-466 4-trifluoromethylcinnamyl Cl H H F I-4674-trifluoromethoxycinnamyl Cl H H F I-468 4-pentafluoroethoxycinnamyl ClH H F I-469 4-methoxycinnamyl Cl H H F I-470 4-ethoxycinnamyl Cl H H FI-471 4-cyanocinnamyl Cl H H F I-472 3-(6-chloro-pyridin-3-yl)-allyl ClH H F I-473 3-(4-chlorophenyl)-but-2-enyl Cl H H F I-4743-(4-chlorophenyl)-3-fluoro- Cl H H F allyl I-4753-chloro-4-fluoro-cinnamyl Cl H H F I-476 3,5-dichloro-cinnamyl Cl H H FI-477 5-phenyl-penta-2,4-dienyl Cl H H F I-4784-isopropyloxycarbonylamino- Cl H H F cinnamyl I-4793-naphthalen-2-yl-allyl Cl H H F I-480 3-(5-trifluoromethyl-pyridin-2-Cl H H F yl)-allyl I-481 3-(5-chloro-pyridin-2-yl)-allyl Cl H H F I-4823-pyridin-4-yl-allyl Cl H H F I-483 3-(2-Chloro-pyridin-4-yl)-allyl Cl HH F I-484 4-chlorobenzyl H Cl H F I-485 Cinnamyl H Cl H F I-4864-chlorocinnamyl H Cl H F I-487 4-fluorocinnamyl H Cl H F I-4884-bromocinnamyl H Cl H F I-489 4-trifluoromethylcinnamyl H Cl H F I-4904-trifluoromethoxycinnamyl H Cl H F I-491 4-pentafluoroethoxycinnamyl HCl H F I-492 4-methoxycinnamyl H Cl H F I-493 4-ethoxycinnamyl H Cl H FI-494 4-cyanocinnamyl H Cl H F I-495 3-(6-chloro-pyridin-3-yl)-allyl HCl H F I-496 3-(4-chlorophenyl)-but-2-enyl H Cl H F I-4973-(4-chlorophenyl)-3-fluoro- H Cl H F allyl I-4983-chloro-4-fluoro-cinnamyl H Cl H F I-499 3,5-dichloro-cinnamyl H Cl H FI-500 5-phenyl-penta-2,4-dienyl H Cl H F I-5014-isopropyloxycarbonylamino- H Cl H F cinnamyl I-5023-naphthalen-2-yl-allyl H Cl H F I-503 3-(5-trifluoromethyl-pyridin-2- HCl H F yl)-allyl I-504 3-(5-chloro-pyridin-2-yl)-allyl H Cl H F I-5053-pyridin-4-yl-allyl H Cl H F I-506 3-(2-Chloro-pyridin-4-yl)-allyl H ClH F I-507 4-chlorobenzyl H H Cl F I-508 Cinnamyl H H Cl F I-5094-chlorocinnamyl H H Cl F I-510 4-fluorocinnamyl H H Cl F I-5114-bromocinnamyl H H Cl F I-512 4-trifluoromethylcinnamyl H H Cl F I-5134-trifluoromethoxycinnamyl H H Cl F I-514 4-pentafluoroethoxycinnamyl HH Cl F I-515 4-methoxycinnamyl H H Cl F I-516 4-ethoxycinnamyl H H Cl FI-517 4-cyanocinnamyl H H Cl F I-518 3-(6-chloro-pyridin-3-yl)-allyl H HCl F I-519 3-(4-chlorophenyl)-but-2-enyl H H Cl F I-5203-(4-chlorophenyl)-3-fluoro- H H Cl F allyl I-5213-chloro-4-fluoro-cinnamyl H H Cl F I-522 3,5-dichloro-cinnamyl H H Cl FI-523 5-phenyl-penta-2,4-dienyl H H Cl F I-5244-isopropyloxycarbonylamino- H H Cl F cinnamyl I-5253-naphthalen-2-yl-allyl H H Cl F I-526 3-(5-trifluoromethyl-pyridin-2- HH Cl F yl)-allyl I-527 3-(5-chloro-pyridin-2-yl)-allyl H H Cl F I-5283-pyridin-4-yl-allyl H H Cl F I-529 3-(2-Chloro-pyridin-4-yl)-allyl H HCl F I-530 4-chlorobenzyl H F F F I-531 Cinnamyl H F F F I-5324-chlorocinnamyl H F F F I-533 4-fluorocinnamyl H F F F I-5344-bromocinnamyl H F F F I-535 4-trifluoromethylcinnamyl H F F F I-5364-trifluoromethoxycinnamyl H F F F I-537 4-pentafluoroethoxycinnamyl H FF F I-538 4-methoxycinnamyl H F F F I-539 4-ethoxycinnamyl H F F F I-5404-cyanocinnamyl H F F F I-541 3-(6-chloro-pyridin-3-yl)-allyl H F F FI-542 3-(4-chlorophenyl)-but-2-enyl H F F F I-5433-(4-chlorophenyl)-3-fluoro- H F F F allyl I-5443-chloro-4-fluoro-cinnamyl H F F F I-545 3,5-dichloro-cinnamyl H F F FI-546 5-phenyl-penta-2,4-dienyl H F F F I-5474-isopropyloxycarbonylamino- H F F F cinnamyl I-5483-naphthalen-2-yl-allyl H F F F I-549 3-(5-trifluoromethyl-pyridin-2- HF F F yl)-allyl I-550 3-(5-chloro-pyridin-2-yl)-allyl H F F F I-5513-pyridin-4-yl-allyl H F F F I-552 3-(2-Chloro-pyridin-4-yl)-allyl H F FF I-553 4-chlorobenzyl F H F F I-554 Cinnamyl F H F F I-5554-chlorocinnamyl F H F F I-556 4-fluorocinnamyl F H F F I-5574-bromocinnamyl F H F F I-558 4-trifluoromethylcinnamyl F H F F I-5594-trifluoromethoxycinnamyl F H F F I-560 4-pentafluoroethoxycinnamyl F HF F I-561 4-methoxycinnamyl F H F F I-562 4-ethoxycinnamyl F H F F I-5634-cyanocinnamyl F H F F I-564 3-(6-chloro-pyridin-3-yl)-allyl F H F FI-565 3-(4-chlorophenyl)-but-2-enyl F H F F I-5663-(4-chlorophenyl)-3-fluoro- F H F F allyl I-5673-chloro-4-fluoro-cinnamyl F H F F I-568 3,5-dichloro-cinnamyl F H F FI-569 5-phenyl-penta-2,4-dienyl F H F F I-5704-isopropyloxycarbonylamino- F H F F cinnamyl I-5713-naphthalen-2-yl-allyl F H F F I-572 3-(5-trifluoromethyl-pyridin-2- FH F F yl)-allyl I-573 3-(5-chloro-pyridin-2-yl)-allyl F H F F I-5743-pyridin-4-yl-allyl F H F F I-575 3-(2-Chloro-pyridin-4-yl)-allyl F H FF I-576 4-chlorobenzyl F F H F I-577 Cinnamyl F F H F I-5784-chlorocinnamyl F F H F I-579 4-fluorocinnamyl F F H F I-5804-bromocinnamyl F F H F I-581 4-trifluoromethylcinnamyl F F H F I-5824-trifluoromethoxycinnamyl F F H F I-583 4-pentafluoroethoxycinnamyl F FH F I-584 4-methoxycinnamyl F F H F I-585 4-ethoxycinnamyl F F H F I-5864-cyanocinnamyl F F H F I-587 3-(6-chloro-pyridin-3-yl)-allyl F F H FI-588 3-(4-chlorophenyl)-but-2-enyl F F H F I-5893-(4-chlorophenyl)-3-fluoro- F F H F allyl I-5903-chloro-4-fluoro-cinnamyl F F H F I-591 3,5-dichloro-cinnamyl F F H FI-592 5-phenyl-penta-2,4-dienyl F F H F I-5934-isopropyloxycarbonylamino- F F H F cinnamyl I-5943-naphthalen-2-yl-allyl F F H F I-595 3-(5-trifluoromethyl-pyridin-2- FF H F yl)-allyl I-596 3-(5-chloro-pyridin-2-yl)-allyl F F H F I-5973-pyridin-4-yl-allyl F F H F I-598 3-(2-Chloro-pyridin-4-yl)-allyl F F HF I-599 4-chlorobenzyl F F F H I-600 Cinnamyl F F F H I-6014-chlorocinnamyl F F F H I-602 4-fluorocinnamyl F F F H I-6034-bromocinnamyl F F F H I-604 4-trifluoromethylcinnamyl F F F H I-6054-trifluoromethoxycinnamyl F F F H I-606 4-pentafluoroethoxycinnamyl F FF H I-607 4-methoxycinnamyl F F F H I-608 4-ethoxycinnamyl F F F H I-6094-cyanocinnamyl F F F H I-610 3-(6-chloro-pyridin-3-yl)-allyl F F F HI-611 3-(4-chlorophenyl)-but-2-enyl F F F H I-6123-(4-chlorophenyl)-3-fluoro- F F F H allyl I-6133-chloro-4-fluoro-cinnamyl F F F H I-614 3,5-dichloro-cinnamyl F F F HI-615 5-phenyl-penta-2,4-dienyl F F F H I-6164-isopropyloxycarbonylamino- F F F H cinnamyl I-6173-naphthalen-2-yl-allyl F F F H I-618 3-(5-trifluoromethyl-pyridin-2- FF F H yl)-allyl I-619 3-(5-chloro-pyridin-2-yl)-allyl F F F H I-6203-pyridin-4-yl-allyl F F F H I-621 3-(2-Chloro-pyridin-4-yl)-allyl F F FH I-622 4-chlorobenzyl H Cl Cl Cl I-623 Cinnamyl H Cl Cl Cl I-6244-chlorocinnamyl H Cl Cl Cl I-625 4-fluorocinnamyl H Cl Cl Cl I-6264-bromocinnamyl H Cl Cl Cl I-627 4-trifluoromethylcinnamyl H Cl Cl ClI-628 4-trifluoromethoxycinnamyl H Cl Cl Cl I-6294-pentafluoroethoxycinnamyl H Cl Cl Cl I-630 4-methoxycinnamyl H Cl ClCl I-631 4-ethoxycinnamyl H Cl Cl Cl I-632 4-cyanocinnamyl H Cl Cl ClI-633 3-(6-chloro-pyridin-3-yl)-allyl H Cl Cl Cl I-6343-(4-chlorophenyl)-but-2-enyl H Cl Cl Cl I-6353-(4-chlorophenyl)-3-fluoro- H Cl Cl Cl allyl I-6363-chloro-4-fluoro-cinnamyl H Cl Cl Cl I-637 3,5-dichloro-cinnamyl H ClCl Cl I-638 5-phenyl-penta-2,4-dienyl H Cl Cl Cl I-6394-isopropyloxycarbonylamino- H Cl Cl Cl cinnamyl I-6403-naphthalen-2-yl-allyl H Cl Cl Cl I-641 3-(5-trifluoromethyl-pyridin-2-H Cl Cl Cl yl)-allyl I-642 3-(5-chloro-pyridin-2-yl)-allyl H Cl Cl ClI-643 3-pyridin-4-yl-allyl H Cl Cl Cl I-6443-(2-Chloro-pyridin-4-yl)-allyl H Cl Cl Cl I-645 4-chlorobenzyl Cl H ClCl I-646 Cinnamyl Cl H Cl Cl I-647 4-chlorocinnamyl Cl H Cl Cl I-6484-fluorocinnamyl Cl H Cl Cl I-649 4-bromocinnamyl Cl H Cl Cl I-6504-trifluoromethylcinnamyl Cl H Cl Cl I-651 4-trifluoromethoxycinnamyl ClH Cl Cl I-652 4-pentafluoroethoxycinnamyl Cl H Cl Cl I-6534-methoxycinnamyl Cl H Cl Cl I-654 4-ethoxycinnamyl Cl H Cl Cl I-6554-cyanocinnamyl Cl H Cl Cl I-656 3-(6-chloro-pyridin-3-yl)-allyl Cl H ClCl I-657 3-(4-chlorophenyl)-but-2-enyl Cl H Cl Cl I-6583-(4-chlorophenyl)-3-fluoro- Cl H Cl Cl allyl I-6593-chloro-4-fluoro-cinnamyl Cl H Cl Cl I-660 3,5-dichloro-cinnamyl Cl HCl Cl I-661 5-phenyl-penta-2,4-dienyl Cl H Cl Cl I-6624-isopropyloxycarbonylamino- Cl H Cl Cl cinnamyl I-6633-naphthalen-2-yl-allyl Cl H Cl Cl I-664 3-(5-trifluoromethyl-pyridin-2-Cl H Cl Cl yl)-allyl I-665 3-(5-chloro-pyridin-2-yl)-allyl Cl H Cl ClI-666 3-pyridin-4-yl-allyl Cl H Cl Cl I-6673-(2-Chloro-pyridin-4-yl)-allyl Cl H Cl Cl I-668 4-chlorobenzyl Cl Cl HCl I-669 Cinnamyl Cl Cl H Cl I-670 4-chlorocinnamyl Cl Cl H Cl I-6714-fluorocinnamyl Cl Cl H Cl I-672 4-bromocinnamyl Cl Cl H Cl I-6734-trifluoromethylcinnamyl Cl Cl H Cl I-674 4-trifluoromethoxycinnamyl ClCl H Cl I-675 4-pentafluoroethoxycinnamyl Cl Cl H Cl I-6764-methoxycinnamyl Cl Cl H Cl I-677 4-ethoxycinnamyl Cl Cl H Cl I-6784-cyanocinnamyl Cl Cl H Cl I-679 3-(6-chloro-pyridin-3-yl)-allyl Cl Cl HCl I-680 3-(4-chlorophenyl)-but-2-enyl Cl Cl H Cl I-6813-(4-chlorophenyl)-3-fluoro- Cl Cl H Cl allyl I-6823-chloro-4-fluoro-cinnamyl Cl Cl H Cl I-683 3,5-dichloro-cinnamyl Cl ClH Cl I-684 5-phenyl-penta-2,4-dienyl Cl Cl H Cl I-6854-isopropyloxycarbonylamino- Cl Cl H Cl cinnamyl I-6863-naphthalen-2-yl-allyl Cl Cl H Cl I-687 3-(5-trifluoromethyl-pyridin-2-Cl Cl H Cl yl)-allyl I-688 3-(5-chloro-pyridin-2-yl)-allyl Cl Cl H ClI-689 3-pyridin-4-yl-allyl Cl Cl H Cl I-6903-(2-Chloro-pyridin-4-yl)-allyl Cl Cl H Cl I-691 4-chlorobenzyl Cl Cl ClH I-692 Cinnamyl Cl Cl Cl H I-693 4-chlorocinnamyl Cl Cl Cl H I-6944-fluorocinnamyl Cl Cl Cl H I-695 4-bromocinnamyl Cl Cl Cl H I-6964-trifluoromethylcinnamyl Cl Cl Cl H I-697 4-trifluoromethoxycinnamyl ClCl Cl H I-698 4-pentafluoroethoxycinnamyl Cl Cl Cl H I-6994-methoxycinnamyl Cl Cl Cl H I-700 4-ethoxycinnamyl Cl Cl Cl H I-7014-cyanocinnamyl Cl Cl Cl H I-702 3-(6-chloro-pyridin-3-yl)-allyl Cl ClCl H I-703 3-(4-chlorophenyl)-but-2-enyl Cl Cl Cl H I-7043-(4-chlorophenyl)-3-fluoro- Cl Cl Cl H allyl I-7053-chloro-4-fluoro-cinnamyl Cl Cl Cl H I-706 3,5-dichloro-cinnamyl Cl ClCl H I-707 5-phenyl-penta-2,4-dienyl Cl Cl Cl H I-7084-isopropyloxycarbonylamino- Cl Cl Cl H cinnamyl I-7093-naphthalen-2-yl-allyl Cl Cl Cl H I-710 3-(5-trifluoromethyl-pyridin-2-Cl Cl Cl H yl)-allyl I-711 3-(5-chloro-pyridin-2-yl)-allyl Cl Cl Cl HI-712 3-pyridin-4-yl-allyl Cl Cl Cl H I-7133-(2-Chloro-pyridin-4-yl)-allyl Cl Cl Cl H I-714 4-chlorobenzyl Cl Cl ClCl I-715 Cinnamyl Cl Cl Cl Cl I-716 4-chlorocinnamyl Cl Cl Cl Cl I-7174-fluorocinnamyl Cl Cl Cl Cl I-718 4-bromocinnamyl Cl Cl Cl Cl I-7194-trifluoromethylcinnamyl Cl Cl Cl Cl I-720 4-trifluoromethoxycinnamylCl Cl Cl Cl I-721 4-pentafluoroethoxycinnamyl Cl Cl Cl Cl I-7224-methoxycinnamyl Cl Cl Cl Cl I-723 4-ethoxycinnamyl Cl Cl Cl Cl I-7244-cyanocinnamyl Cl Cl Cl Cl I-725 3-(6-chloro-pyridin-3-yl)-allyl Cl ClCl Cl I-726 3-(4-chlorophenyl)-but-2-enyl Cl Cl Cl Cl I-7273-(4-chlorophenyl)-3-fluoro- Cl Cl Cl Cl allyl I-7283-chloro-4-fluoro-cinnamyl Cl Cl Cl Cl I-729 3,5-dichloro-cinnamyl Cl ClCl Cl I-730 5-phenyl-penta-2,4-dienyl Cl Cl Cl Cl I-7314-isopropyloxycarbonylamino- Cl Cl Cl Cl cinnamyl I-7323-naphthalen-2-yl-allyl Cl Cl Cl Cl I-7333-(5-trifluoromethyl-pyridin-2- Cl Cl Cl Cl yl)-allyl I-7343-(5-chloro-pyridin-2-yl)-allyl Cl Cl Cl Cl I-735 3-pyridin-4-yl-allylCl Cl Cl Cl I-736 3-(2-Chloro-pyridin-4-yl)-allyl Cl Cl Cl Cl I-7374-chlorobenzyl F F F F I-738 Cinnamyl F F F F I-739 4-chlorocinnamyl F FF F I-740 4-fluorocinnamyl F F F F I-741 4-bromocinnamyl F F F F I-7424-trifluoromethylcinnamyl F F F F I-743 4-trifluoromethoxycinnamyl F F FF I-744 4-pentafluoroethoxycinnamyl F F F F I-745 4-methoxycinnamyl F FF F I-746 4-ethoxycinnamyl F F F F I-747 4-cyanocinnamyl F F F F I-7483-(6-chloro-pyridin-3-yl)-allyl F F F F I-7493-(4-chlorophenyl)-but-2-enyl F F F F I-750 3-(4-chlorophenyl)-3-fluoro-F F F F allyl I-751 3-chloro-4-fluoro-cinnamyl F F F F I-7523,5-dichloro-cinnamyl F F F F I-753 5-phenyl-penta-2,4-dienyl F F F FI-754 4-isopropyloxycarbonylamino- F F F F cinnamyl I-7553-naphthalen-2-yl-allyl F F F F I-756 3-(5-trifluoromethyl-pyridin-2- FF F F yl)-allyl I-757 3-(5-chloro-pyridin-2-yl)-allyl F F F F I-7583-pyridin-4-yl-allyl F F F F I-759 3-(2-Chloro-pyridin-4-yl)-allyl F F FF I-760 4-chlorobenzyl H F H F I-761 Cinnamyl H F H F I-7624-chlorocinnamyl H F H F I-763 4-fluorocinnamyl H F H F I-7644-bromocinnamyl H F H F I-765 4-trifluoromethylcinnamyl H F H F I-7664-trifluoromethoxycinnamyl H F H F I-767 4-pentafluoroethoxycinnamyl H FH F I-768 4-methoxycinnamyl H F H F I-769 4-ethoxycinnamyl H F H F I-7704-cyanocinnamyl H F H F I-771 3-(6-chloro-pyridin-3-yl)-allyl H F H FI-772 3-(4-chlorophenyl)-but-2-enyl H F H F I-7733-(4-chlorophenyl)-3-fluoro- H F H F allyl I-7743-chloro-4-fluoro-cinnamyl H F H F I-775 3,5-dichloro-cinnamyl H F H FI-776 5-phenyl-penta-2,4-dienyl H F H F I-7774-isopropyloxycarbonylamino- H F H F cinnamyl I-778 3-naphthalen-2-yl-allyl H F H F I-779 3-(5-trifluoromethyl-pyridin-2- H FH F yl)-allyl I-780 3-(5-chloro-pyridin-2-yl)-allyl H F H F I-7813-pyridin-4-yl-allyl H H H F I-782 3-(2-Chloro-pyridin-4-yl)-allyl H F HF I-783 4-chlorobenzyl H F F H I-784 Cinnamyl H F F H I-7854-chlorocinnamyl H F F H I-786 4-fluorocinnamyl H F F H I-7874-bromocinnamyl H F F H I-788 4-trifluoromethylcinnamyl H F F H I-7894-trifluoromethoxycinnamyl H F F H I-790 4-pentafluoroethoxycinnamyl H FF H I-791 4-methoxycinnamyl H F F H I-792 4-ethoxycinnamyl H F F H I-7934-cyanocinnamyl H F F H I-794 3-(6-chloro-pyridin-3-yl)-allyl H F F HI-795 3-(4-chlorophenyl)-but-2-enyl H F F H I-7963-(4-chlorophenyl)-3-fluoro- H F F H allyl I-7973-chloro-4-fluoro-cinnamyl H F F H I-798 3,5-dichloro-cinnamyl H F F HI-799 5-phenyl-penta-2,4-dienyl H F F H I-8004-isopropyloxycarbonylamino- H F F H cinnamyl I-8013-naphthalen-2-yl-allyl H F F H I-802 3-(5-trifluoromethyl-pyridin-2- HF F H yl)-allyl I-803 3-(5-chloro-pyridin-2-yl)-allyl H F F H I-8043-pyridin-4-yl-allyl H F F H I-805 3-(2-Chloro-pyridin-4-yl)-allyl H F FH I-806 4-chlorobenzyl H F F H I-807 Cinnamyl H H F F I-8084-chlorocinnamyl H H F F I-809 4-fluorocinnamyl H H F F I-8104-bromocinnamyl H H F F I-811 4-trifluoromethylcinnamyl H H F F I-8124-trifluoromethoxycinnamyl H H F F I-813 4-pentafluoroethoxycinnamyl H HF F I-814 4-methoxycinnamyl H H F F I-815 4-ethoxycinnamyl H H F F I-8164-cyanocinnamyl H H F F I-817 3-(6-chloro-pyridin-3-yl)-allyl H H F FI-818 3-(4-chlorophenyl)-but-2-enyl H H F F I-8193-(4-chlorophenyl)-3-fluoro- H H F F allyl I-8203-chloro-4-fluoro-cinnamyl H H F F I-821 3,5-dichloro-cinnamyl H H F FI-822 5-phenyl-penta-2,4-dienyl H H F F I-8234-isopropyloxycarbonylamino- H H F F cinnamyl I-8243-naphthalen-2-yl-allyl H H F F I-825 3-(5-trifluoromethyl-pyridin-2- HH F F yl)-allyl I-826 3-(5-chloro-pyridin-2-yl)-allyl H H F F I-8273-pyridin-4-yl-allyl H H F F I-828 3-(2-Chloro-pyridin-4-yl)-allyl H H FF I-829 4-chlorobenzyl H H Cl Cl I-830 Cinnamyl H H Cl Cl I-8314-chlorocinnamyl H H Cl Cl I-832 4-fluorocinnamyl H H Cl Cl I-8334-bromocinnamyl H H Cl Cl I-834 4-trifluoromethylcinnamyl H H Cl ClI-835 4-trifluoromethoxycinnamyl H H Cl Cl I-8364-pentafluoroethoxycinnamyl H H Cl Cl I-837 4-methoxycinnamyl H H Cl ClI-838 4-ethoxycinnamyl H H Cl Cl I-839 4-cyanocinnamyl H H Cl Cl I-8403-(6-chloro-pyridin-3-yl)-allyl H H Cl Cl I-8413-(4-chlorophenyl)-but-2-enyl H H Cl Cl I-8423-(4-chlorophenyl)-3-fluoro- H H Cl Cl allyl I-8433-chloro-4-fluoro-cinnamyl H H Cl Cl I-844 3,5-dichloro-cinnamyl H H ClCl I-845 5-phenyl-penta-2,4-dienyl H H Cl Cl I-8464-isopropyloxycarbonylamino- H H Cl Cl cinnamyl I-8473-naphthalen-2-yl-allyl H H Cl Cl I-848 3-(5-trifluoromethyl-pyridin-2-H H Cl Cl yl)-allyl I-849 3-(5-chloro-pyridin-2-yl)-allyl H H Cl ClI-850 3-pyridin-4-yl-allyl H H Cl Cl I-8513-(2-Chloro-pyridin-4-yl)-allyl H H Cl Cl I-852 4-chlorobenzyl H Cl Cl HI-853 Cinnamyl H Cl Cl H I-854 4-chlorocinnamyl H Cl Cl H I-8554-fluorocinnamyl H Cl Cl H I-856 4-bromocinnamyl H Cl Cl H I-8574-trifluoromethylcinnamyl H Cl Cl H I-858 4-trifluoromethoxycinnamyl HCl Cl H I-859 4-pentafluoroethoxycinnamyl H Cl Cl H I-8604-methoxycinnamyl H Cl Cl H I-861 4-ethoxycinnamyl H Cl Cl H I-8624-cyanocinnamyl H Cl Cl H I-863 3-(6-chloro-pyridin-3-yl)-allyl H Cl ClH I-864 3-(4-chlorophenyl)-but-2-enyl H Cl Cl H I-8653-(4-chlorophenyl)-3-fluoro- H Cl Cl H allyl I-8663-chloro-4-fluoro-cinnamyl H Cl Cl H I-867 3,5-dichloro-cinnamyl H Cl ClH I-868 5-phenyl-penta-2,4-dienyl H Cl Cl H I-8694-isopropyloxycarbonylamino- H Cl Cl H cinnamyl I-8703-naphthalen-2-yl-allyl H Cl Cl H I-871 3-(5-trifluoromethyl-pyridin-2-H Cl Cl H yl)-allyl I-872 3-(5-chloro-pyridin-2-yl)-allyl H Cl Cl HI-873 3-pyridin-4-yl-allyl H Cl Cl H I-8743-(2-Chloro-pyridin-4-yl)-allyl H Cl Cl H I-875 4-chlorobenzyl H Cl H ClI-876 Cinnamyl H Cl H Cl I-877 4-chlorocinnamyl H Cl H Cl I-8784-fluorocinnamyl H Cl H Cl I-879 4-bromocinnamyl H Cl H Cl I-8804-trifluoromethylcinnamyl H Cl H Cl I-881 4-trifluoromethoxycinnamyl HCl H Cl I-882 4-pentafluoroethoxycinnamyl H Cl H Cl I-8834-methoxycinnamyl H Cl H Cl I-884 4-ethoxycinnamyl H Cl H Cl I-8854-cyanocinnamyl H Cl H Cl I-886 3-(6-chloro-pyridin-3-yl)-allyl H Cl HCl I-887 3-(4-chlorophenyl)-but-2-enyl H Cl H Cl I-8883-(4-chlorophenyl)-3-fluoro- H Cl H Cl allyl I-8893-chloro-4-fluoro-cinnamyl H Cl H Cl I-890 3,5-dichloro-cinnamyl H Cl HCl I-891 5-phenyl-penta-2,4-dienyl H Cl H Cl I-8924-isopropyloxycarbonylamino- H Cl H Cl cinnamyl I-8933-naphthalen-2-yl-allyl H Cl H Cl I-894 3-(5-trifluoromethyl-pyridin-2-H Cl H Cl yl)-allyl I-895 3-(5-chloro-pyridin-2-yl)-allyl H Cl H ClI-896 3-pyridin-4-yl-allyl H Cl H Cl I-8973-(2-Chloro-pyridin-4-yl)-allyl H Cl H Cl

Table II provides 897 compounds of formula Ib

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table III provides 897 compounds of formula Ic

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1

Table IV provides 897 compounds of formula Id

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1

Table V provides 897 compounds of formula Ie

wherein and the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) aregiven in Table 1

Table VI provides 897 compounds of formula If

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1

Table VII provides 897 compounds of formula Ig

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table VIII provides 897 compounds of formula Ih

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1

Table IX provides 897 compounds of formula Ii

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table X provides 897 compounds of formula Ij

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XI provides 897 compounds of formula Ik

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XIII provides 897 compounds of formula Im

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XIV provides 897 compounds of formula In

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XV provides 897 compounds of formula Io

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XVI provides 897 compounds of formula Ip

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XVII provides 897 compounds of formula Iq

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XIX provides 897 compounds of formula Ir

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XIX provides 897 compounds of formula Is

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XX provides 897 compounds of formula It

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XXI provides 897 compounds of formula Iu

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XXII provides 897 compounds of formula Iv

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

Table XXIII provides 897 compounds of formula Iw

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.Table XXIV provides 110 compounds of formula Ix

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 24.

TABLE 24 Compound No R⁸ R^(4b) R^(4c) R^(4d) XXIV-1 Cinnamyl H H HXXIV-2 4-chlorocinnamyl H H H XXIV-3 4-fluorocinnamyl H H H XXIV-44-bromocinnamyl H H H XXIV-5 4-trifluoromethylcinnamyl H H H XXIV-64-trifluoromethoxycinnamyl H H H XXIV-7 4-pentafluoroethoxycinnamyl H HH XXIV-8 4-methoxycinnamyl H H H XXIV-9 4-ethoxycinnamyl H H H XXIV-104-cyanocinnamyl H H H XXIV-11 3-(6-chloro-pyridin-3-yl)-allyl H H HXXIV-12 3-(4-chlorophenyl)-but-2-enyl H H H XXIV-133-(4-chlorophenyl)-3-fluoro-allyl H H H XXIV-143-chloro-4-fluoro-cinnamyl H H H XXIV-15 3,5-dichloro-cinnamyl H H HXXIV-16 5-phenyl-penta-2,4-dienyl H H H XXIV-174-isopropyloxycarbonylamino-cinnamyl H H H XXIV-183-naphthalen-2-yl-allyl H H H XXIV-193-(5-trifluoromethyl-pyridin-2-yl)-allyl H H H XXIV-203-(5-chloro-pyridin-2-yl)-allyl H H H XXIV-21 3-pyridin-4-yl-allyl H H HXXIV-22 3-(2-Chloro-pyridin-4-yl)-allyl H H H XXIV-23 Cinnamyl F H HXXIV-24 4-chlorocinnamyl F H H XXIV-25 4-fluorocinnamyl F H H XXIV-264-bromocinnamyl F H H XXIV-27 4-trifluoromethylcinnamyl F H H XXIV-284-trifluoromethoxycinnamyl F H H XXIV-29 4-pentafluoroethoxycinnamyl F HH XXIV-30 4-methoxycinnamyl F H H XXIV-31 4-ethoxycinnamyl F H H XXIV-324-cyanocinnamyl F H H XXIV-33 3-(6-chloro-pyridin-3-yl)-allyl F H HXXIV-34 3-(4-chlorophenyl)-but-2-enyl F H H XXIV-353-(4-chlorophenyl)-3-fluoro-allyl F H H XXIV-363-chloro-4-fluoro-cinnamyl F H H XXIV-37 3,5-dichloro-cinnamyl F H HXXIV-38 5-phenyl-penta-2,4-dienyl F H H XXIV-394-isopropyloxycarbonylamino-cinnamyl F H H XXIV-403-naphthalen-2-yl-allyl F H H XXIV-413-(5-trifluoromethyl-pyridin-2-yl)-allyl F H H XXIV-423-(5-chloro-pyridin-2-yl)-allyl F H H XXIV-43 3-pyridin-4-yl-allyl F H HXXIV-44 3-(2-Chloro-pyridin-4-yl)-allyl F H H XXIV-45 Cinnamyl Cl H HXXIV-46 4-chlorocinnamyl Cl H H XXIV-47 4-fluorocinnamyl Cl H H XXIV-484-bromocinnamyl Cl H H XXIV-49 4-trifluoromethylcinnamyl Cl H H XXIV-504-trifluoromethoxycinnamyl Cl H H XXIV-51 4-pentafluoroethoxycinnamyl ClH H XXIV-52 4-methoxycinnamyl Cl H H XXIV-53 4-ethoxycinnamyl Cl H HXXIV-54 4-cyanocinnamyl Cl H H XXIV-55 3-(6-chloro-pyridin-3-yl)-allylCl H H XXIV-56 3-(4-chlorophenyl)-but-2-enyl Cl H H XXIV-573-(4-chlorophenyl)-3-fluoro-allyl Cl H H XXIV-583-chloro-4-fluoro-cinnamyl Cl H H XXIV-59 3,5-dichloro-cinnamyl Cl H HXXIV-60 5-phenyl-penta-2,4-dienyl Cl H H XXIV-614-isopropyloxycarbonylamino-cinnamyl Cl H H XXIV-623-naphthalen-2-yl-allyl Cl H H XXIV-633-(5-trifluoromethyl-pyridin-2-yl)-allyl Cl H H XXIV-643-(5-chloro-pyridin-2-yl)-allyl Cl H H XXIV-65 3-pyridin-4-yl-allyl Cl HH XXIV-66 3-(2-Chloro-pyridin-4-yl)-allyl Cl H H XXIV-67 Cinnamyl H F HXXIV-68 4-chlorocinnamyl H F H XXIV-69 4-fluorocinnamyl H F H XXIV-704-bromocinnamyl H F H XXIV-71 4-trifluoromethylcinnamyl H F H XXIV-724-trifluoromethoxycinnamyl H F H XXIV-73 4-pentafluoroethoxycinnamyl H FH XXIV-74 4-methoxycinnamyl H F H XXIV-75 4-ethoxycinnamyl H F H XXIV-764-cyanocinnamyl H F H XXIV-77 3-(6-chloro-pyridin-3-yl)-allyl H F HXXIV-78 3-(4-chlorophenyl)-but-2-enyl H F H XXIV-793-(4-chlorophenyl)-3-fluoro-allyl H F H XXIV-803-chloro-4-fluoro-cinnamyl H F H XXIV-81 3,5-dichloro-cinnamyl H F HXXIV-82 5-phenyl-penta-2,4-dienyl H F H XXIV-834-isopropyloxycarbonylamino-cinnamyl H F H XXIV-843-naphthalen-2-yl-allyl H F H XXIV-853-(5-trifluoromethyl-pyridin-2-yl)-allyl H F H XXIV-863-(5-chloro-pyridin-2-yl)-allyl H F H XXIV-87 3-pyridin-4-yl-allyl H F HXXIV-88 3-(2-Chloro-pyridin-4-yl)-allyl H F H XXIV-89 Cinnamyl H Cl HXXIV-90 4-chlorocinnamyl H Cl H XXIV-91 4-fluorocinnamyl H Cl H XXIV-924-bromocinnamyl H Cl H XXIV-93 4-trifluoromethylcinnamyl H Cl H XXIV-944-trifluoromethoxycinnamyl H Cl H XXIV-95 4-pentafluoroethoxycinnamyl HCl H XXIV-96 4-methoxycinnamyl H Cl H XXIV-97 4-ethoxycinnamyl H Cl HXXIV-98 4-cyanocinnamyl H Cl H XXIV-99 3-(6-chloro-pyridin-3-yl)-allyl HCl H XXIV-100 3-(4-chlorophenyl)-but-2-enyl H Cl H XXIV-1013-(4-chlorophenyl)-3-fluoro-allyl H Cl H XXIV-1023-chloro-4-fluoro-cinnamyl H Cl H XXIV-103 3,5-dichloro-cinnamyl H Cl HXXIV-104 5-phenyl-penta-2,4-dienyl H Cl H XXIV-1054-isopropyloxycarbonylamino-cinnamyl H Cl H XXIV-1063-naphthalen-2-yl-allyl H Cl H XXIV-1073-(5-trifluoromethyl-pyridin-2-yl)-allyl H Cl H XXIV-1083-(5-chloro-pyridin-2-yl)-allyl H Cl H XXIV-109 3-pyridin-4-yl-allyl HCl H XXIV-110 3-(2-Chloro-pyridin-4-yl)-allyl H Cl HTable XXV provides 897 compounds of formula Iy

wherein the values of R⁸, R^(4a), R^(4b), R^(4c) and R^(4d) are given inTable 1.

The compounds of the invention may be made by a variety of methods. Forexample they may be prepared according to the reactions of Scheme 1.

Thus a compound of formula 1 may be obtained from a compound of formula2 by reaction with a suitable electrophilic species. Compounds offormula 1 where Y is a carbonyl group may be formed by the reaction ofcompounds of formula 2 with a carboxylic acid derivative of formulaR1-C(O)—Z where Z is chloride, hydroxy, alkoxy or acyloxy at atemperature between 0° C. and 150° C. optionally in an organic solventsuch as dichloromethane, chloroform or 1,2-dichloroethane, optionally inthe presence of a tertiary amine base such as triethylamine ordiisopropylethylamine and optionally in the presence of a coupling agentsuch as dicyclohexylcarbodiimide. Compounds of formula 1 where Y is acarbonyl group and R1 is an amino substituent of formula R′—NH— may beformed by the reaction of compounds of formula 4 with an isocyanate offormula R′—N═C═O under similar conditions. Compounds of formula 1 whereY is a group of formula S(O)_(m) may be formed from compounds of formula2 by treatment with compounds of formula of R1-S(O)_(m)—Cl under similarconditions. Compounds of formula 1 where Y is a thiocarbonyl group andR1 is an amino substituent of formula R′—NH— may be formed by thereaction of compounds of formula 2 with an isothiocyanate of formulaR′—N═C═S under similar conditions.

Alternatively compounds of formula 1 where Y is a thiocarbonyl group andR1 is a carbon substituent may be formed by treatment of compounds offormula 1 where Y is a carbonyl group and R1 is a carbon substituentwith a suitable thionating agent such as Lawesson's reagent.

In the above procedures, acid derivatives of the formula R1-C(O)—Z,isocyanates of formula R′—N═C═O, isothiocyanates of formula R′—N═C═S andsulfur electrophiles of formula R1-S(O)_(q)—Cl are either knowncompounds or may be formed from known compounds by known methods by aperson skilled in the art.

Compounds of formula 2 may be prepared from compounds of formula 3 byreduction of the nitro group, according to known methods by a personskilled in the art.

Compounds of formula 3 may be obtained from compounds of formula 6 whereP is H by reaction with an alkylating agent of the formula R8-L, where Lis chloride, bromide, iodide or a sulfonate (e.g. mesylate or tosylate)or similar leaving group at a temperature of between ambient temperatureand 100° C., typically 65° C., in an organic solvent such asdichloromethane, chloroform or 1,2-dichloroethane in the presence of atertiary amine base such as triethylamine or diisopropylethylamine andoptionally catalysed by halide salts such as sodium iodide, potassiumiodide or tetrabutylammonium iodide. Alternatively, a compound offormula 6 where P is H may be reacted with an aldehyde of the formulaRzCHO at a temperature between ambient temperature and 100° C. in anorganic solvent such as tetrahydrofuran or ethanol or mixtures ofsolvents in the presence of a reducing agent such as borane-pyridinecomplex, sodium borohydride, sodium (triacetoxy)borohydride, sodiumcyanoborohydride or such like, to produce a compound of formula 3 whereR8 is CH₂—Rz.

Alternatively, a compound of formula 1 may be obtained from a compoundof formula 4 by (1) reaction with an acid such as trifluoroacetic acidat ambient temperature in an organic solvent such as dichloromethane,chloroform or 1,2-dichloroethane followed by neutralisation of thereaction mixture with an aqueous solution of an inorganic base such assodium carbonate, sodium bicarbonate or similar compound; then (2)reaction with an alkylating agent or an aldehyde as described above.

Compounds of formula 4 may be formed by reaction of compounds of formula5 with a suitable electrophile, as described above in the method forconverting compounds of formula 2 to compounds of formula 1.

Compounds of formula 5 may be obtained from compounds of formula 6 whereP is t-butoxycarbonyl by reduction of the nitro group according to knownmethods.

Compounds of formula 6 may be obtained from compounds of formula 7 byreaction with piperazine (P═H) or N—BOC-piperazine (P=t-butoxycarbonyl)at a temperature between 0° C. and 180° C., in a solvent such asdichloromethane, 1,2-dichloroethane, acetonitrile, dimethylformamide ordimethylsulfoxide in the presence of a base such as triethylamine,diisopropylethylamine or potassium carbonate or in the absence of base.

Compounds of formula 5, formula 6 and formula 7 are known compounds ormay be made from known compounds by known methods.

Certain compounds of formula 2, formula 3 and formula 4 are novel and assuch form a further aspect of the invention.

The skilled person will readily recognise that it is possible to convertone compound of formula 1 wherein R2 is H or an intermediate of Scheme 1to other compounds of formula I. Examples of such transformations aregiven in Schemes 2, 3 and 4 in which the R groups have the meanings asdefined for a compound of formula I above.

The compounds of formula (I) can be used to combat and controlinfestations of insect pests such as Lepidoptera, Diptera, Hemiptera,Thysanoptera, Orthoptera, Dictyoptera, Coleoptera, Siphonaptera,Hymenoptera and Isoptera and also other invertebrate pests, for example,acarine, nematode and mollusc pests. Insects, acarines, nematodes andmolluscs are hereinafter collectively referred to as pests. The pestswhich may be combated and controlled by the use of the inventioncompounds include those pests associated with agriculture (which termincludes the growing of crops for food and fibre products), horticultureand animal husbandry, companion animals, forestry and the storage ofproducts of vegetable origin (such as fruit, grain and timber); thosepests associated with the damage of man-made structures and thetransmission of diseases of man and animals; and also nuisance pests(such as flies).

Examples of pest species which may be controlled by the compounds offormula (I) include: Myzus persicae (aphid), Aphis gossypii (aphid),Aphis fabae (aphid), Lygus spp. (capsids), Dysdercus spp. (capsids),Nilaparvata lugens (planthopper), Nephotettixc incticeps (leafhopper),Nezara spp. (stinkbugs), Euschistus spp. (stinkbugs), Leptocorisa spp.(stinkbugs), Frankliniella occidentalis (thrip), Thrips spp. (thrips),Leptinotarsa decemlineata (Colorado potato beetle), Anthonomus grandis(boll weevil), Aonidiella spp. (scale insects), Trialeurodes spp. (whiteflies), Bemisia tabaci (white fly), Ostrinia nubilalis (European cornborer), Spodoptera littoralis (cotton leafworm), Heliothis virescens(tobacco budworm), Helicoverpa armigera (cotton bollworm), Helicoverpazea (cotton bollworm), Sylepta derogata (cotton leaf roller), Pierisbrassicae (white butterfly), Plutella xylostella (diamond back moth),Agrotis spp. (cutworms), Chilo suppressalis (rice stem borer), Locustamigratoria (locust), Chortiocetes terminifera (locust), Diabrotica spp.(rootworms), Panonychus ulmi (European red mite), Panonychus citri(citrus red mite), Tetranychus urticae (two-spotted spider mite),Tetranychus cinnabarinus (carmine spider mite), Phyllocoptruta oleivora(citrus rust mite), Polyphagotarsonemus latus (broad mite), Brevipalpusspp. (flat mites), Boophilus microplus (cattle tick), Dermacentorvariabilis (American dog tick), Ctenocephalides felis (cat flea),Liriomyza spp. (leafminer), Musca domestica (housefly), Aedes aegypti(mosquito), Anopheles spp. (mosquitoes), Culex spp. (mosquitoes),Lucillia spp. (blowflies), Blattella germanica (cockroach), Periplanetaamericana (cockroach), Blatta orientalis (cockroach), termites of theMastotermitidae (for example Mastotermes spp.), the Kalotermitidae (forexample Neotermes spp.), the Rhinotermitidae (for example Coptotermesformosanus, Reticulitermes flavipes, R. speratu, R. virginicus, R.hesperus, and R. santonensis) and the Termitidae (for exampleGlobitermes sulphureus), Solenopsis geminata (fire ant), Monomoriumpharaonis (pharaoh's ant), Damalinia spp. and Linognathus spp. (bitingand sucking lice), Meloidogyne spp. (root knot nematodes), Globoderaspp. and Heterodera spp. (cyst nematodes), Pratylenchus spp. (lesionnematodes), Rhodopholus spp. (banana burrowing nematodes), Tylenchulusspp. (citrus nematodes), Haemonchus contortus (barber pole worm),Caenorhabditis elegans (vinegar eelworm), Trichostrongylus spp. (gastrointestinal nematodes) and Deroceras reticulatum (slug).

The invention therefore provides a method of combating and controllinginsects, acarines, nematodes or molluscs which comprises applying aninsecticidally, acaricidally, nematicidally or molluscicidally effectiveamount of a compound of formula (I), or a composition containing acompound of formula (I), to a pest, a locus of pest, or to a plantsusceptible to attack by a pest, The compounds of formula (I) arepreferably used against insects, acarines or nematodes.

The term “plant” as used herein includes seedlings, bushes and trees.

In order to apply a compound of formula (I) as an insecticide,acaricide, nematicide or molluscicide to a pest, a locus of pest, or toa plant susceptible to attack by a pest, a compound of formula (I) isusually formulated into a composition which includes, in addition to thecompound of formula (I), a suitable inert diluent or carrier and,optionally, a surface active agent (SFA). SFAs are chemicals which areable to modify the properties of an interface (for example,liquid/solid, liquid/air or liquid/liquid interfaces) by lowering theinterfacial tension and thereby leading to changes in other properties(for example dispersion, emulsification and wetting). It is preferredthat all compositions (both solid and liquid formulations) comprise, byweight, 0.0001 to 95%, more preferably 1 to 85%, for example 5 to 60%,of a compound of formula (I). The composition is generally used for thecontrol of pests such that a compound of formula (I) is applied at arate of from 0.1 g to 10 kg per hectare, preferably from 1 g to 6 kg perhectare, more preferably from 1 g to 1 kg per hectare.

When used in a seed dressing, a compound of formula (I) is used at arate of 0.0001 g to 10 g (for example 0.001 g or 0.05 g), preferably0.005 g to 10 g, more preferably 0.005 g to 4 g, per kilogram of seed.

In another aspect the present invention provides an insecticidal,acaricidal, nematicidal or molluscicidal composition comprising aninsecticidally, acaricidally, nematicidally or molluscicidally effectiveamount of a compound of formula (I) and a suitable carrier or diluenttherefor. The composition is preferably an insecticidal, acaricidal,nematicidal or molluscicidal composition.

In a still further aspect the invention provides a method of combatingand controlling pests at a locus which comprises treating the pests orthe locus of the pests with an insecticidally, acaricidally,nematicidally or molluscicidally effective amount of a compositioncomprising a compound of formula (I). The compounds of formula (I) arepreferably used against insects, acarines or nematodes.

The compositions can be chosen from a number of formulation types,including dustable powders (DP), soluble powders (SP), water solublegranules (SG), water dispersible granules (WG), wettable powders (WP),granules (GR) (slow or fast release), soluble concentrates (SL), oilmiscible liquids (OL), ultra low volume liquids (UL), emulsifiableconcentrates (EC), dispersible concentrates (DC), emulsions (both oil inwater (EW) and water in oil (EO)), micro-emulsions (ME), suspensionconcentrates (SC), aerosols, fogging/smoke formulations, capsulesuspensions (CS) and seed treatment formulations. The formulation typechosen in any instance will depend upon the particular purpose envisagedand the physical, chemical and biological properties of the compound offormula (I).

Dustable powders (DP) may be prepared by mixing a compound of formula(I) with one or more solid diluents (for example natural clays, kaolin,pyrophyllite, bentonite, alumina, montmorillonite, kieselguhr, chalk,diatomaceous earths, calcium phosphates, calcium and magnesiumcarbonates, sulphur, lime, flours, talc and other organic and inorganicsolid carriers) and mechanically grinding the mixture to a fine powder.

Soluble powders (SP) may be prepared by mixing a compound of formula (I)with one or more water-soluble inorganic salts (such as sodiumbicarbonate, sodium carbonate or magnesium sulphate) or one or morewater-soluble organic solids (such as a polysaccharide) and, optionally,one or more wetting agents, one or more dispersing agents or a mixtureof said agents to improve water dispersibility/solubility. The mixtureis then ground to a fine powder. Similar compositions may also begranulated to form water soluble granules (SG).

Wettable powders (WP) may be prepared by mixing a compound of formula(I) with one or more solid diluents or carriers, one or more wettingagents and, preferably, one or more dispersing agents and, optionally,one or more suspending agents to facilitate the dispersion in liquids.The mixture is then ground to a fine powder. Similar compositions mayalso be granulated to form water dispersible granules (WG).

Granules (GR) may be formed either by granulating a mixture of acompound of formula (I) and one or more powdered solid diluents orcarriers, or from pre-formed blank granules by absorbing a compound offormula (I) (or a solution thereof, in a suitable agent) in a porousgranular material (such as pumice, attapulgite clays, fuller's earth,kieselguhr, diatomaceous earths or ground corn cobs) or by adsorbing acompound of formula (I) (or a solution thereof, in a suitable agent) onto a hard core material (such as sands, silicates, mineral carbonates,sulphates or phosphates) and drying if necessary. Agents which arecommonly used to aid absorption or adsorption include solvents (such asaliphatic and aromatic petroleum solvents, alcohols, ethers, ketones andesters) and sticking agents (such as polyvinyl acetates, polyvinylalcohols, dextrins, sugars and vegetable oils). One or more otheradditives may also be included in granules (for example an emulsifyingagent, wetting agent or dispersing agent).

Dispersible Concentrates (DC) may be prepared by dissolving a compoundof formula (I) in water or an organic solvent, such as a ketone, alcoholor glycol ether. These solutions may contain a surface active agent (forexample to improve water dilution or prevent crystallisation in a spraytank).

Emulsifiable concentrates (EC) or oil-in-water emulsions (EW) may beprepared by dissolving a compound of formula (I) in an organic solvent(optionally containing one or more wetting agents, one or moreemulsifying agents or a mixture of said agents). Suitable organicsolvents for use in ECs include aromatic hydrocarbons (such asalkylbenzenes or alkylnaphthalenes, exemplified by SOLVESSO 100,SOLVESSO 150 and SOLVESSO 200; SOLVESSO is a Registered Trade Mark),ketones (such as cyclohexanone or methylcyclohexanone) and alcohols(such as benzyl alcohol, furfuryl alcohol or butanol),N-alkylpyrrolidones (such as N-methylpyrrolidone or N-octylpyrrolidone),dimethyl amides of fatty acids (such as C₈-C₁₀ fatty acid dimethylamide)and chlorinated hydrocarbons. An EC product may spontaneously emulsifyon addition to water, to produce an emulsion with sufficient stabilityto allow spray application through appropriate equipment. Preparation ofan EW involves obtaining a compound of formula (I) either as a liquid(if it is not a liquid at room temperature, it may be melted at areasonable temperature, typically below 70° C.) or in solution (bydissolving it in an appropriate solvent) and then emulsifiying theresultant liquid or solution into water containing one or more SFAs,under high shear, to produce an emulsion. Suitable solvents for use inEWs include vegetable oils, chlorinated hydrocarbons (such aschlorobenzenes), aromatic solvents (such as alkylbenzenes oralkylnaphthalenes) and other appropriate organic solvents which have alow solubility in water.

Microemulsions (ME) may be prepared by mixing water with a blend of oneor more solvents with one or more SFAs, to produce spontaneously athermodynamically stable isotropic liquid formulation. A compound offormula (I) is present initially in either the water or the solvent/SFAblend. Suitable solvents for use in MEs include those hereinbeforedescribed for use in in ECs or in EWs. An ME may be either anoil-in-water or a water-in-oil system (which system is present may bedetermined by conductivity measurements) and may be suitable for mixingwater-soluble and oil-soluble pesticides in the same formulation. An MEis suitable for dilution into water, either remaining as a microemulsionor forming a conventional oil-in-water emulsion.

Suspension concentrates (SC) may comprise aqueous or non-aqueoussuspensions of finely divided insoluble solid particles of a compound offormula (I). SCs may be prepared by ball or bead milling the solidcompound of formula (I) in a suitable medium, optionally with one ormore dispersing agents, to produce a fine particle suspension of thecompound. One or more wetting agents may be included in the compositionand a suspending agent may be included to reduce the rate at which theparticles settle. Alternatively, a compound of formula (I) may be drymilled and added to water, containing agents hereinbefore described, toproduce the desired end product.

Aerosol formulations comprise a compound of formula (I) and a suitablepropellant (for example n-butane). A compound of formula (I) may also bedissolved or dispersed in a suitable medium (for example water or awater miscible liquid, such as n-propanol) to provide compositions foruse in non-pressurised, hand-actuated spray pumps.

A compound of formula (I) may be mixed in the dry state with apyrotechnic mixture to form a composition suitable for generating, in anenclosed space, a smoke containing the compound.

Capsule suspensions (CS) may be prepared in a manner similar to thepreparation of EW formulations but with an additional polymerisationstage such that an aqueous dispersion of oil droplets is obtained, inwhich each oil droplet is encapsulated by a polymeric shell and containsa compound of formula (I) and, optionally, a carrier or diluenttherefor. The polymeric shell may be produced by either an interfacialpolycondensation reaction or by a coacervation procedure. Thecompositions may provide for controlled release of the compound offormula (I) and they may be used for seed treatment. A compound offormula (I) may also be formulated in a biodegradable polymeric matrixto provide a slow, controlled release of the compound.

A composition may include one or more additives to improve thebiological performance of the composition (for example by improvingwetting, retention or distribution on surfaces; resistance to rain ontreated surfaces; or uptake or mobility of a compound of formula (I)).Such additives include surface active agents, spray additives based onoils, for example certain mineral oils or natural plant oils (such assoy bean and rape seed oil), and blends of these with otherbio-enhancing adjuvants (ingredients which may aid or modify the actionof a compound of formula (I)).

A compound of formula (I) may also be formulated for use as a seedtreatment, for example as a powder composition, including a powder fordry seed treatment (DS), a water soluble powder (SS) or a waterdispersible powder for slurry treatment (WS), or as a liquidcomposition, including a flowable concentrate (FS), a solution (LS) or acapsule suspension (CS). The preparations of DS, SS, WS, FS and LScompositions are very similar to those of, respectively, DP, SP, WP, SCand DC compositions described above. Compositions for treating seed mayinclude an agent for assisting the adhesion of the composition to theseed (for example a mineral oil or a film-forming barrier).

Wetting agents, dispersing agents and emulsifying agents may be surfaceSFAs of the cationic, anionic, amphoteric or non-ionic type.

Suitable SFAs of the cationic type include quaternary ammonium compounds(for example cetyltrimethyl ammonium bromide), imidazolines and aminesalts.

Suitable anionic SFAs include alkali metals salts of fatty acids, saltsof aliphatic monoesters of sulphuric acid (for example sodium laurylsulphate), salts of sulphonated aromatic compounds (for example sodiumdodecylbenzenesulphonate, calcium dodecylbenzenesulphonate,butylnaphthalene sulphonate and mixtures of sodium di-isopropyl- andtri-isopropyl-naphthalene sulphonates), ether sulphates, alcohol ethersulphates (for example sodium laureth-3-sulphate), ether carboxylates(for example sodium laureth-3-carboxylate), phosphate esters (productsfrom the reaction between one or more fatty alcohols and phosphoric acid(predominately mono-esters) or phosphorus pentoxide (predominatelydi-esters), for example the reaction between lauryl alcohol andtetraphosphoric acid; additionally these products may be ethoxylated),sulphosuccinamates, paraffin or olefine sulphonates, taurates andlignosulphonates.

Suitable SFAs of the amphoteric type include betaines, propionates andglycinates.

Suitable SFAs of the non-ionic type include condensation products ofalkylene oxides, such as ethylene oxide, propylene oxide, butylene oxideor mixtures thereof, with fatty alcohols (such as oleyl alcohol or cetylalcohol) or with alkylphenols (such as octylphenol, nonylphenol oroctylcresol); partial esters derived from long chain fatty acids orhexitol anhydrides; condensation products of said partial esters withethylene oxide; block polymers (comprising ethylene oxide and propyleneoxide); alkanolamides; simple esters (for example fatty acidpolyethylene glycol esters); amine oxides (for example lauryl dimethylamine oxide); and lecithins.

Suitable suspending agents include hydrophilic colloids (such aspolysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose)and swelling clays (such as bentonite or attapulgite).

A compound of formula (I) may be applied by any of the known means ofapplying pesticidal compounds. For example, it may be applied,formulated or unformulated, to the pests or to a locus of the pests(such as a habitat of the pests, or a growing plant liable toinfestation by the pests) or to any part of the plant, including thefoliage, stems, branches or roots, to the seed before it is planted orto other media in which plants are growing or are to be planted (such assoil surrounding the roots, the soil generally, paddy water orhydroponic culture systems), directly or it may be sprayed on, dustedon, applied by dipping, applied as a cream or paste formulation, appliedas a vapour or applied through distribution or incorporation of acomposition (such as a granular composition or a composition packed in awater-soluble bag) in soil or an aqueous environment.

A compound of formula (I) may also be injected into plants or sprayedonto vegetation using electrodynamic spraying techniques or other lowvolume methods, or applied by land or aerial irrigation systems.

Compositions for use as aqueous preparations (aqueous solutions ordispersions) are generally supplied in the form of a concentratecontaining a high proportion of the active ingredient, the concentratebeing added to water before use. These concentrates, which may includeDCs, SCs, ECs, EWs, MEs SGs, SPs, WPs, WGs and CSs, are often requiredto withstand storage for prolonged periods and, after such storage, tobe capable of addition to water to form aqueous preparations whichremain homogeneous for a sufficient time to enable them to be applied byconventional spray equipment. Such aqueous preparations may containvarying amounts of a compound of formula (I) (for example 0.0001 to 10%,by weight) depending upon the purpose for which they are to be used.

A compound of formula (I) may be used in mixtures with fertilisers (forexample nitrogen-, potassium- or phosphorus-containing fertilisers).Suitable formulation types include granules of fertiliser. The mixturessuitably contain up to 25% by weight of the compound of formula (I).

The invention therefore also provides a fertiliser compositioncomprising a fertiliser and a compound of formula (I).

The compositions of this invention may contain other compounds havingbiological activity, for example micronutrients or compounds havingfungicidal activity or which possess plant growth regulating,herbicidal, insecticidal, nematicidal or acaricidal activity.

The compound of formula (I) may be the sole active ingredient of thecomposition or it may be admixed with one or more additional activeingredients such as a pesticide, fungicide, synergist, herbicide orplant growth regulator where appropriate. An additional activeingredient may: provide a composition having a broader spectrum ofactivity or increased persistence at a locus; synergise the activity orcomplement the activity (for example by increasing the speed of effector overcoming repellency) of the compound of formula (I); or help toovercome or prevent the development of resistance to individualcomponents. The particular additional active ingredient will depend uponthe intended utility of the composition. Examples of suitable pesticidesinclude the following:

a) Pyrethroids, such as permethrin, cypermethrin, fenvalerate,esfenvalerate, deltamethrin, cyhalothrin (in particularlambda-cyhalothrin), bifenthrin, fenpropathrin, cyfluthrin, tefluthrin,fish safe pyrethroids (for example ethofenprox), natural pyrethrin,tetramethrin, s-bioallethrin, fenfluthrin, prallethrin or5-benzyl-3-furylmethyl-(E)-(1R,3S)-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate;b) Organophosphates, such as, profenofos, sulprofos, acephate, methylparathion, azinphos-methyl, demeton-s-methyl, heptenophos, thiometon,fenamiphos, monocrotophos, profenofos, triazophos, methamidophos,dimethoate, phosphamidon, malathion, chlorpyrifos, phosalone, terbufos,fensulfothion, fonofos, phorate, phoxim, pirimiphos-methyl,pirimiphos-ethyl, fenitrothion, fosthiazate or diazinon;c) Carbamates (including aryl carbamates), such as pirimicarb,triazamate, cloethocarb, carbofuran, furathiocarb, ethiofencarb,aldicarb, thiofurox, carbosulfan, bendiocarb, fenobucarb, propoxur,methomyl or oxamyl;d) Benzoyl ureas, such as diflubenzuron, triflumuron, hexaflumuron,flufenoxuron or chlorfluazuron;e) Organic tin compounds, such as cyhexatin, fenbutatin oxide orazocyclotin;f) Pyrazoles, such as tebufenpyrad and fenpyroximate;g) Macrolides, such as avermectins or milbemycins, for exampleabamectin, emamectin benzoate, ivermectin, milbemycin, spinosad orazadirachtin;h) Hormones or pheromones;i) Organochlorine compounds such as endosulfan, benzene hexachloride,DDT, chlordane or dieldrin;j) Amidines, such as chlordimeform or amitraz;k) Fumigant agents, such as chloropicrin, dichloropropane, methylbromide or metam;l) Chloronicotinyl compounds such as imidacloprid, thiacloprid,acetamiprid, nitenpyram or thiamethoxam;m) Diacylhydrazines, such as tebufenozide, chromafenozide ormethoxyfenozide;n) Diphenyl ethers, such as diofenolan or pyriproxifen;o) Indoxacarb;p) Chlorfenapyr; orq) Pymetrozine.

In addition to the major chemical classes of pesticide listed above,other pesticides having particular targets may be employed in thecomposition, if appropriate for the intended utility of the composition.For instance, selective insecticides for particular crops, for examplestemborer specific insecticides (such as cartap) or hopper specificinsecticides (such as buprofezin) for use in rice may be employed.Alternatively insecticides or acaricides specific for particular insectspecies/stages may also be included in the compositions (for exampleacaricidal ovo-larvicides, such as clofentezine, flubenzimine,hexythiazox or tetradifon; acaricidal motilicides, such as dicofol orpropargite; acaricides, such as bromopropylate or chlorobenzilate; orgrowth regulators, such as hydramethylnon, cyromazine, methoprene,chlorfluazuron or diflubenzuron).

Examples of fungicidal compounds which may be included in thecomposition of the invention are(E)-N-methyl-2-[2-(2,5-dimethylphenoxymethyl)phenyl]-2-methoxy-iminoacetamide(SSF-129),4-bromo-2-cyano-N,N-dimethyl-6-trifluoromethylbenzimidazole-1-sulphonamide,α-[N-(3-chloro-2,6-xylyl)-2-methoxyacetamido]-γ-butyrolactone,4-chloro-2-cyano-N,N-dimethyl-5-p-tolylimidazole-1-sulfonamide (IKF-916,cyamidazosulfamid),3-5-dichloro-N-(3-chloro-1-ethyl-1-methyl-2-oxopropyl)-4-methylbenzamide(RH-7281, zoxamide),N-allyl-4,5,-dimethyl-2-trimethylsilylthiophene-3-carboxamide(MON65500),N-(1-cyano-1,2-dimethylpropyl)-2-(2,4-dichlorophenoxy)propionamide(AC382042), N-(2-methoxy-5-pyridyl)-cyclopropane carboxamide,acibenzolar (CGA245704), alanycarb, aldimorph, anilazine, azaconazole,azoxystrobin, benalaxyl, benomyl, biloxazol, bitertanol, blasticidin S,bromuconazole, bupirimate, captafol, captan, carbendazim, carbendazimchlorhydrate, carboxin, carpropamid, carvone, CGA41396, CGA41397,chinomethionate, chlorothalonil, chlorozolinate, clozylacon, coppercontaining compounds such as copper oxychloride, copper oxyquinolate,copper sulphate, copper tallate and Bordeaux mixture, cymoxanil,cyproconazole, cyprodinil, debacarb, di-2-pyridyl disulphide1,1′-dioxide, dichlofluanid, diclomezine, dicloran, diethofencarb,difenoconazole, difenzoquat, diflumetorim, O,O-di-iso-propyl-5-benzylthiophosphate, dimefluazole, dimetconazole, dimethomorph, dimethirimol,diniconazole, dinocap, dithianon, dodecyl dimethyl ammonium chloride,dodemorph, dodine, doguadine, edifenphos, epoxiconazole, ethirimol,ethyl(Z)—N-benzyl-N([methyl(methyl-thioethylideneaminooxycarbonyl)amino]thio)-β-alaninate,etridiazole, famoxadone, fenamidone (RPA407213), fenarimol,fenbuconazole, fenfuram, fenhexamid (KBR2738), fenpiclonil, fenpropidin,fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzone,fluazinam, fludioxonil, flumetover, fluoroimide, fluquinconazole,flusilazole, flutolanil, flutriafol, folpet, fuberidazole, furalaxyl,furametpyr, guazatine, hexaconazole, hydroxyisoxazole, hymexazole,imazalil, imibenconazole, iminoctadine, iminoctadine triacetate,ipconazole, iprobenfos, iprodione, iprovalicarb (SZX0722), isopropanylbutyl carbamate, isoprothiolane, kasugamycin, kresoxim-methyl, LY186054,LY211795, LY248908, mancozeb, maneb, mefenoxam, mepanipyrim, mepronil,metalaxyl, metconazole, metiram, metiram-zinc, metominostrobin,myclobutanil, neoasozin, nickel dimethyldithiocarbamate,nitrothal-isopropyl, nuarimol, ofurace, organomercury compounds,oxadixyl, oxasulfuron, oxolinic acid, oxpoconazole, oxycarboxin,pefurazoate, penconazole, pencycuron, phenazin oxide, phosetyl-Al,phosphorus acids, phthalide, picoxystrobin (ZA1963), polyoxin D,polyram, probenazole, prochloraz, procymidone, propamocarb,propiconazole, propineb, propionic acid, pyrazophos, pyrifenox,pyrimethanil, pyroquilon, pyroxyfur, pyrroInitrin, quaternary ammoniumcompounds, quinomethionate, quinoxyfen, quintozene, sipconazole (F-155),sodium pentachlorophenate, spiroxamine, streptomycin, sulphur,tebuconazole, tecloftalam, tecnazene, tetraconazole, thiabendazole,thifluzamid, 2-(thiocyanomethylthio)benzothiazole, thiophanate-methyl,thiram, timibenconazole, tolclofos-methyl, tolylfluanid, triadimefon,triadimenol, triazbutil, triazoxide, tricyclazole, tridemorph,trifloxystrobin (CGA279202), triforine, triflumizole, triticonazole,validamycin A, vapam, vinclozolin, zineb and ziram.

The compounds of formula (I) may be mixed with soil, peat or otherrooting media for the protection of plants against seed-borne,soil-borne or foliar fungal diseases.

Examples of suitable synergists for use in the compositions includepiperonyl butoxide, sesamex, safroxan and dodecyl imidazole.

Suitable herbicides and plant-growth regulators for inclusion in thecompositions will depend upon the intended target and the effectrequired.

An example of a rice selective herbicide which may be included ispropanil. An example of a plant growth regulator for use in cotton isPIX™.

Some mixtures may comprise active ingredients which have significantlydifferent physical, chemical or biological properties such that they donot easily lend themselves to the same conventional formulation type. Inthese circumstances other formulation types may be prepared. Forexample, where one active ingredient is a water insoluble solid and theother a water insoluble liquid, it may nevertheless be possible todisperse each active ingredient in the same continuous aqueous phase bydispersing the solid active ingredient as a suspension (using apreparation analogous to that of an SC) but dispersing the liquid activeingredient as an emulsion (using a preparation analogous to that of anEW). The resultant composition is a suspoemulsion (SE) formulation.

The invention is illustrated by the following Examples:

Mass spectra data were obtained for selected compounds of the followingexamples using LCMS: LC5: 254 nm-gradient 10% A to 100% B A=H2O+0.01%HCOOH B═CH₃CN/CH₃₀H+0.01% HCOOH positive electrospray 150-1000 m/z.

EXAMPLE 1

This Example illustrates the preparation of2-chloro-N-(4-chloro-2-{4-[(E)-3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}-phenyl)-isonicotinamide.

Step A: Triethylamine (4.2 ml) was added to a stirred solution of2,4-dichloronitrobenzene (1.9 g) and 1-t-butoxycarbonyl-piperazine (2.2g) in dimethylsulfoxide (18 ml) under N₂. The resulting solution wasstirred at 70° C. for 48 hours then cooled to room temperature. Waterwas added and the mixture extracted three times with ethyl acetate; thecombined organic layers were dried over sodium sulfate and concentratedin vacuo. The residue was subjected to silica gel chromatography(cyclohexane:ethyl acetate 8:2) to afford4-(5-chloro-2-nitrophenyl)-piperazine-1-carboxylic acid tert-butyl ester(2.6 g) as a foam. ¹H NMR (400 MHz, CDCl₃) 1.5 (s, 9H), 2.9 (br s, 4H),3.5 (br s, 4H), 6.9 (d, J=10 Hz, 1H), 7.0 (s, 1H), 7.7 (d, J=10 Hz, 1H);MS (ES+) 242/244 (M+H⁺—CO₂-isobutene), 286/288 (M+H⁺-isobutene).

Step B: To a stirred suspension of the compound obtained in Step A (2.5g) in ethanol (40 ml) and water (30 ml) at 60° C. was added sodiumdithionite (7.6 g). The resulting mixture was stirred at 60° C. for 1hour then ethanol was removed in vacuo. The suspension was extractedthree times with ethyl acetate, the combined organic layers were driedover sodium sulfate and concentrated in vacuo. The residue was subjectedto silica gel chromatography (cyclohexane:ethyl acetate 1:1) to afford4-(2-Amino-5-chloro-phenyl)-piperazine-1-carboxylic acid tert-butylester (1.0 g) as white crystals. M.p. 125-127° C.; ¹H NMR (400 MHz,CDCl₃) 1.5 (s, 9H), 2.8 (m, 4H), 3.5 (m, 4H), 3.9 (s, 2H), 6.6 (d, J=10Hz, 1H), 6.8 (d, J=10 Hz, 1H), 6.9 (s, 1H); MS (ES+) 212/214(M+H⁺—CO₂-isobutene), 256/258 (M+H⁺-isobutene), 312/314 (M+H⁺).

Step C: triethylamine (2 ml) was added to a stirred solution of thecompound obtained in Step B (1.0 g) in dichloromethane (20 ml); thesolution was cooled to 0° C. and 2-chloroisonicotinoyl chloride (1.2 g)was added. The resulting mixture was stirred at room temperature for 12hours, poured into water, extracted two times with dichloromethane, thecombined organic layers were dried over sodium sulfate and concentratedin vacuo. The residue was subjected to silica gel chromatography(cyclohexane:ethyl acetate 7:2) to afford4-{5-Chloro-2-[(2-chloro-pyridine-4-carbonyl)-amino]-phenyl}-piperazine-1-carboxylicacid tert-butyl ester, which was recrystallised (845 mg) fromhexane/ethyl acetate to give white crystals. M.p. 185-189° C.; ¹H NMR(400 MHz, CDCl₃) 1.5 (s, 9H), 2.9 (m, 4H), 3.7 (m, 4H), 7.2 (d, J=1.5Hz, 1H), 7.2 (dd, J=1.5, 10 Hz, 1H), 7.6 (d, J=5.5 Hz, 1H), 7.8 (s, 1H),8.5 (d, J=10 Hz, 1H), 8.63 (d, J=5.5 Hz, 1H), 9.4 (s, 1H, NH); MS (ES+)351/353 (M+H⁺—CO₂-isobutene), 395/397 (M+H⁺-isobutene), 451/453 (M+H⁺).

Step D: A solution of the compound obtained in Step C (200 mg) indichloromethane (10 ml) was treated with trifluoroacetic acid (0.3 ml)for 48 hours at room temperature. The reaction mixture was basified withsaturated aqueous sodium bicarbonate, extracted two times withdichloromethane, the organic layer was dried over sodium sulfate andconcentrated in vacuo. The residue was dissolved in acetonitrile (20ml), diisopropylethylamine (0.16 ml) and 4-chlorocinnamyl chloride (96mg) were added. The solution was stirred 50 hours at room temperature,the solvent was removed in vacuo and the residue was subjected to silicagel chromatography (cyclohexane:ethyl acetate 7:2) to afford the titleproduct (162 mg) as a yellow solid. M.p. 129-132° C.; ¹H NMR (400 MHz,CDCl₃) 2.7 (m, 4H), 2.9 (m, 4H), 3.2 (d, J=9 Hz, 2H), 6.2 (dt, J=18, 9Hz, 1H), 6.5 (d, J=18 Hz, 1H), 7.1-7.3 (m, 6H), 7.6 (d, J=5.5 Hz, 1H),7.70 (s, 1H), 8.4 (d, J=10 Hz, 1H), 8.5 (d, J=5.5 Hz, 1H), 9.4 (s, 1H,NH); Retention Time HPLC 2.46 min; MS (ES+) 501/503/505 (M+H⁺).

The following compounds were prepared according to procedures analogousto those described in Example 1:

Retention M.p Time Compound Name Structure (° C.) MH⁺ (min)2-chloro-N-(2-{4-[(E)- 3-(4-chloro-phenyl)- allyl]-piperazin-1-yl}-phenyl)- isonicotinamide

467/469 2.26 2-chloro-N-(2-{4-[(E)- 3-(4-trifluoromethyl-phenyl)-allyl]- piperazin-1-yl}- phenyl)- isonicotinamide

501 2.32 2-chloro-N-(2-{4-[(E)- 3-(4-trifluoromethoxy- phenyl)-allyl]-piperazin-1-yl}- phenyl)- isonicotinamide

517 2.46 2-chloro-N-(4-fluoro-2- {4-[(E)-3-(4-chloro- phenyl)-allyl]-piperazin-1-yl}- phenyl)- isonicotinamide

145-147 485/487 2.29 2-chloro-N-(4-fluoro-2- {4-[(E)-3-(4-trifluoromethyl- phenyl)-allyl]- piperazin-1-yl}- phenyl)-isonicotinamide

 98-100 519 1.91 2-chloro-N-(4-fluoro-2- {4-[(E)-3-(4- trifluoromethoxy-phenyl)-allyl]- piperazin-1-yl}- phenyl)- isonicotinamide

 85-89 535/537 2.44 2-chloro-N-(5-fluoro-2- {4-[(E)-3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- phenyl)- isonicotinamide

 80-83 485/487 2.28 2-chloro-N-(5-fluoro-2- {4-[(E)-3-(4-trifluoromethyl- phenyl)-allyl]- piperazin-1-yl}- phenyl)-isonicotinamide

105-109 519 2.51 2-chloro-N-(5-fluoro-2- {4-[(E)-3-(4- trifluoromethoxy-phenyl)-allyl]- piperazin-1-yl}- phenyl)- isonicotinamide

110-114 535 2.48 2-chloro-N-(4-chloro- 2-{4-[(E)-3-(4- trifluoromethyl-phenyl)-allyl]- piperazin-1-yl}- phenyl)- isonicotinamide

129-131 535/537 2.56 2-chloro-N-(4-chloro- 2-{4-[(E)-3-(4-trifluoromethoxy- phenyl)-allyl]- piperazin-1-yl}- phenyl)-isonicotinamide

 92-95 551/553 2.63 2-chloro-N-(3,4- dichloro-2-{4-[(E)-3-(4-chloro-phenyl)- allyl]-piperazin-1-yl}- phenyl)- isonicotinamide

154-156 537/539 2.38 2,6-dichloro-N-(3,4- dichloro-2-{4-[(E)-3-(4-chloro-phenyl)- allyl]-piperazin-1-yl}- phenyl)- isonicotinamide

178-181 571/573 2.67 N-(4-chloro-2-{4-[(E)- 3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}- phenyl)-benzamide

 79-81 466/468 2.49 N-(4-chloro-2-{4-[(E)- 3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}- phenyl)- isonicotinamide

152-154 467-469 2.11 2,6-dichloro-N-(4- chloro-2-{4-[(E)-3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}-phenyl)- isonicotinamide

121-123 537/539 2.77 6-chloro-N-(4-chloro- 2-{4-[(E)-3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- phenyl)-nicotinamide

120-123 467/469 2.10 N-(4-chloro-2-{4-[(E)- 3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}- phenyl)-4- trifluoromethoxy- benzamide

104-107 550/552 3.22 N-(4-chloro-2-{4-[(E)- 3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}- phenyl)-4-chloro- benzamide

 62-64 502/504 2.85 N-(4-chloro-2-{4-[(E)- 3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}- phenyl)-acetamide

145-148 404/406 1.95 cyclopropanecarboxylic acid (4-chloro-2-{4-[(E)-3-(4-chloro- phenyl)-allyl]- piperazin-1-yl}- phenyl)-amide

 87-89 430/432 2.17 (4-chloro-2-{4-[(E)-3- (4-chloro-phenyl)-allyl]-piperazin-1-yl}- phenyl)-carbamic acid methyl ester

 73-76 420/422 2.17 2-fluoro-N-(4-chloro-2- {4-[(E)-3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- phenyl)- isonicotinamide

162-165 485/487 2.31 2-(3-chloro-pyridin-2- yl)-5-trifluoromethyl-2H-pyrazole-3- carboxylic acid (4- chloro-2-{4-[(E)-3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- phenyl)-amide

 97-100 637/639 2.65 2-chloro-N-(4-chloro- 5-trifluoromethyl-2-{4-[(E)-3-(4-chloro- phenyl)-allyl]- piperazin-1-yl}- phenyl)-isonicotinamide

135-136 569/571 2.92 2-Chloro-N-{4-chloro- 2-[4-(4-chloro-benzyl)-piperazin-1-yl]- phenyl}- isonicotinamide

116-118 475/477 2.50 N-(4-Chloro-2-{4-[(E)- 3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}- phenyl)- methanesulfonamide

 81-83 440-442 2.01

EXAMPLE 2

This Example illustrates the preparation of2-chloro-N-(2-{4-[(E)-3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}-phenyl)-N-methyl-isonicotinamide.

4-{2-[(2-chloro-pyridine-4-carbonyl)-amino]-phenyl}-piperazine-1-carboxylicacid tert-butyl ester (100 mg, prepared as described in Example 1, StepsA-C) was added to a suspension of sodium hydride (50% in oil, 24 mg) intetrahydrofuran at 0° C. and the resulting mixture was stirred at 0° C.for 1 hour at which time iodomethane (0.03 ml) was added. The reactionmixture was stirred at room temperature for 3 hours, diluted with ethylacetate, washed three times with water, dried over sodium sulfate andconcentrated in vacuo. The residue was subjected to silica gelchromatography (cyclohexane:ethyl acetate 7:3) to afford4-{2-[(2-Chloro-pyridine-4-carbonyl)-methyl-amino]-phenyl}-piperazine-1-carboxylicacid tert-butyl ester as white crystals. M.p. 59-61° C.; ¹H NMR (400MHz, CDCl₃) 1.5 (s, 9H), 2.2 (m, 2H), 2.8 (m, 2H), 3.4 (m, 2H), 3.4 (s,3H), 3.5 (m, 2H), 6.7 (m, 1H), 6.9 (m, 1H), 7.0-7.3 (m, 4H), 8.1 (m,1H); MS (ES+) 331 (M+H⁺—CO₂-isobutene), 375 (M+H⁺-isobutene), 431(M+H⁺). This compound was treated according to Example 1 Step D toafford the title product as yellow crystals. M.p. 117-120° C.; ¹H NMR(400 MHz, CDCl₃) 2.4 (m, 2H), 2.5 (m, 2H), 2.6 (m, 2H), 2.9 (m, 2H), 3.2(m, 2H), 3.5 (s, 3H), 3.5 (m, 2H), 6.2 (dt, J=18, 9 Hz, 1H), 6.5 (d,J=18 Hz, 1H), 6.8 (d, J=9 Hz, 1H), 6.9 (d, J=5 Hz, 1H), 7.0-7.3 (m, 6H),8.1 (d, J=5 Hz, 1H); retention Time HPLC 2.17 min; MS (ES+) 481/483(M+H⁺).

The following compounds were prepared according to procedures analogousto those described in Example 2:

Retention M.p Time Compound Name Structure (° C.) MH⁺ (min)2-chloro-N-(5-fluoro- 2-{4-[(E)-3-(4-chloro- phenyl)-allyl]-piperazin-1-yl}- phenyl)-N-methyl- isonicotinamide

 60-64 499/501 2.12 2-chloro-N-(4-fluoro- 2-{4-[(E)-3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- phenyl)-N-methyl- isonicotinamide

110-117 499/501 2.09 2-chloro-N-(4-chloro- 2-{4-[(E)-3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- phenyl)-N-methyl- isonicotinamide

130-133 517-519 2.28 2-chloro-N-(3,4- dichloro-2-{4-[(E)-3-(4-chloro-phenyl)- allyl]-piperazin-1-yl}- phenyl)-N-methyl-isonicotinamide

112-115 551/553 2.42

EXAMPLE 3

This Example illustrates the preparation of2-Chloro-N-[4-chloro-2-(4-methyl-piperazin-1-yl)-phenyl]-isonicotinamide.

Step A: A solution of4-{5-chloro-2-[(2-chloro-pyridine-4-carbonyl)-amino]-phenyl}-piperazine-1-carboxylicacid tert-butyl ester (6.7 g, Example 1, Step C) in dichloromethane (20ml) was treated with trifluoroacetic acid (10 ml) for 20 hours at roomtemperature. Concentration of the solution under reduced pressureafforded 2-chloro-N-[4-chloro-2-(piperazin-1-yl)-phenyl]-isonicotinamidetrifluoroacetate (6.9 g) as a brown solid. MS (ES+) 351/353 (M+H⁺).

Step B: The product obtained in Step A (300 mg), formic acid (16 ml) and37% aqueous formaldehyde (0.47 ml) were refluxed for 2 hours. Thereaction mixture was diluted with water, made basic with saturatedaqueous sodium bicarbonate and extracted with ethyl acetate. The organiclayer was dried over sodium sulfate and concentrated in vacuo. Theresidue was subjected to silica gel chromatography (ethylacetate:methanol 8:2) to afford the title product. M.p. 118-120° C.; ¹HNMR (400 MHz, CDCl₃) 2.4 (s, 3H), 2.7 (m, 2H), 3.0 (m, 4H), 7.2 (m, 2H),7.6 (d, J=5.0 Hz, 1H), 7.7 (s, 1H), 8.4 (d, J=9.0 Hz, 1H), 8.5 (d, J=5.0Hz, 1H), 9.4 (br s, 1H); MS (ES+) 365/367 (M+H⁺).

EXAMPLE 4

This Example illustrates the preparation of1-(2-{4-[(E)-3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}-4-fluoro-phenyl)-3-(3-methoxy-propyl)-urea.

Step A: A solution of 4-(5-fluoro-2-nitrophenyl)-piperazine-1-carboxylicacid tert-butyl ester (10 g, prepared from 2,4-difluoronitrobenzene asdescribed in Example 1, Step A) in dichloromethane (80 ml) was treatedwith trifluoroacetic acid (23 ml) for 24 hours at room temperature. Thereaction mixture was concentrated in vacuo. The residue was dissolved inacetonitrile (100 ml), diisopropylethylamine (27 ml) and4-chloro-cinnamyl chloride (6.8 g) were added. The solution was stirredfor 17 hours at room temperature, the solvent was removed in vacuo andthe residue was subjected to silica gel chromatography(cyclohexane:ethyl acetate 1:1) to afford1-[(E)-3-(4-chloro-phenyl)-allyl]-4-(5-fluoro-2-nitro-phenyl)-piperazine(10.5 g); ¹H NMR (400 MHz, CDCl₃) 2.7 (t, J=8 Hz, 4H), 3.1 (t, J=8 Hz,4H), 3.2 (d, J=9 Hz, 2H), 6.2 (dt, J=18, 9 Hz, 1H), 6.5 (d, J=18 Hz,1H), 6.6 (dt, J=1.0, 7.0 Hz, 1H), 6.7 (dd, J=1.0, 10 Hz, 1H), 7.2-7.3(m, 4H), 7.8 (d, J=7.0, 10.0 Hz, 1H); MS (ES+) 151/153, 376/378 (M+H⁺).

Step B: To a stirred suspension of the compound obtained in Step A (8.0g) in ethanol (66 ml) and water (80 ml) at 60° C. was added sodiumdithionite (11 g). The resulting mixture was stirred at 60° C. for 1hour then ethanol was removed in vacuo. The suspension was extractedthree times with ethyl acetate, the combined organic layers were driedover sodium sulfate and concentrated in vacuo. The residue was filteredon silica gel (eluent ethyl acetate) to afford1-[(E)-3-(4-chloro-phenyl)-allyl]-4-(5-fluoro-2-amino-phenyl)-piperazine(4.1 g). ¹H NMR (400 MHz, CDCl₃) 2.6 (m, 4H), 2.9 (m, 4H), 3.2 (d, J=9Hz, 2H), 3.7 (m, 2H), 6.2 (dt, J=18, 9 Hz, 1H), 6.5 (d, J=18 Hz, 1H),6.6 (m, 2H), 6.7 (d, J=10 Hz, 1H), 7.2-7.3 (m, 4H); MS (ES+) 151/153,346/348 (M+H⁺).

Step C: To a stirred solution of di-tert-butyl carbonate (266 mg) indichloromethane (4 ml) under nitrogen was added 4-dimethylaminopyridine(106 mg) in dichloromethane (4 ml) followed by the product obtained inStep B (300 mg). The solution was stirred at room temperature until gasevolution ceased. 3-Methoxypropylamine (155 mg) dissolved indichloromethane (4 ml) was then added dropwise and the resultingsolution stirred at room temperature for 1 hour. The solvent was removedunder reduced pressure and the residue purified by silica gelchromatography (cyclohexane:ethyl acetate 1:9) to afford the titleproduct (210 mg). M.p. 86-90° C.; ¹H NMR (400 MHz, CDCl₃) 1.8 (quint,J=7 Hz, 2H), 2.6 (m, 4H), 2.9 (m, 4H), 3.2 (d, J=9 Hz, 2H), 3.2 (s, 3H),3.3 (q, J=7 Hz, 2H), 3.4 (t, J=7 Hz, 2H), 5.3 (m, 1H), 6.2 (dt, J=18, 9Hz, 1H), 6.5 (d, J=18 Hz, 1H), 6.8 (m, 2H), 6.9 (s, 1H), 7.2-7.3 (m,6H), 7.7 (m, 1H); Retention Time HPLC 1.93; MS (ES+) 372/374, 461/463(M+H⁺).

The following compounds were prepared according to procedures analogousto those described in Example 4:

Retention M.p Time Compound Name Structure (° C.) MH⁺ (min)1-(4-Chloro-2-{4-[(E)- 3-(4-chloro-phenyl)- allyl]-piperazin-1-yl}-phenyl)-3-(2-methoxy- ethyl)-urea

178 463/465 1.97 1-(2-{4-[(E)-3-(4- chloro-phenyl)-allyl]-piperazin-1-yl}-4- fluoro-phenyl)-3-(2- chloro-thiazol-5- ylmethyl)-urea

 94-98 520/522 2.12 1-(2-{4-[(E)-3-(4- chloro-phenyl)-allyl]-piperazin-1-yl}-4- fluoro-phenyl)-3-(2- [1,3]dioxolan-2-yl- ethyl)-urea

 76-80 489 2.02 1-(2-{4-[(E)-3-(4- chloro-phenyl)-allyl]-piperazin-1-yl}-4- fluoro-phenyl)-3- isopropyl-urea

162-166 431 2.08

EXAMPLE 5

This Example illustrates the preparation of1-(2-{4-[(E)-3-(4-Chloro-phenyl)-allyl]-piperazin-1-yl}-4-fluoro-phenyl)-3-(2-chloro-thiazol-5-ylmethyl)-imidazolidin-2-one.

Step A: To a solution of1-[(E)-3-(4-chloro-phenyl)-allyl]-4-(5-fluoro-2-amino-phenyl)-piperazine(1.0 g, Example 3, Step B) in tetrahydrofuran (10 ml) at 0° C. was added2-chloroethylisocyanate (327 mg) and the resulting solution was stirredunder nitrogen at room temperature for 18 hours. The residue wasdissolved in a minimum volume of tetrahydrofuran, then added to asuspension of sodium hydride (146 mg, 50% in oil) in tetrahydrofuran (10ml). The reaction mixture was stirred at room temperature for 3 hours,concentrated under reduced pressure, then triturated with diethyl etherto afford1-(2-{4-[(E)-3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}-4-fluoro-phenyl)-imidazolidin-2-one(677 mg) as white crystals. M.p. 170-172° C.; ¹H NMR (400 MHz, CDCl₃)2.7 (m, 4H), 3.11 (m, 4H), 3.26 (d, J=6.8 Hz, 2H), 3.63 (t, J=5.7 Hz,2H), 3.99 (t, J=5.7 Hz, 2H), 5.12 (br s, 1H), 6.32 (dt, J=15.6, 6.8 Hz,1H), 6.57 (d, J=15.6 Hz, 1H), 6.82 (m, 2H), 7.3-7.4 (m, 4H); MS (ES+)415/417 (M+H⁺).

Step B: The product obtained in Step A (250 mg) dissolved indimethylacetamide (4 ml) was added to a suspension of sodium hydride(50% in oil, 29 mg) in dimethylacetamide (4 ml) at 0° C. and theresulting mixture was stirred at 0° C. for 30 min at which timeC-(2-chloro-thiazol-5-yl)-methylamine (102 mg) dissolved indimethylacetamide (4 ml) was added. The reaction mixture was stirred atroom temperature for 2 hours, quenched by addition of water, extractedwith ethyl acetate (three times), dried over sodium sulfate andconcentrated in vacuo. The residue was subjected to silica gelchromatography (cyclohexane:ethyl acetate 1:9) to afford the titleproduct as a yellow solid. M.p. 72-77° C.; ¹H NMR (400 MHz, CDCl₃) 2.7(m, 4H), 3.0 (m, 4H), 3.2 (d, J=7 Hz, 2H), 3.35 (t, J=6 Hz, 2H), 3.8 (t,J=6 Hz, 2H), 4.5 (s, 2H), 6.3 (dt, J=16, 7 Hz, 1H), 6.5 (d, J=16 Hz,1H), 6.8 (m, 2H), 7.2-7.3 (m, 4H), 7.4 (s, 1H); MS (ES+) 546/548 (M+H⁺).

EXAMPLE 6

This Example illustrates the preparation of2-chloro-N-(5-chloro-2-{4-[(E)-3-(4-trifluoromethyl-phenyl)-allyl]-piperazin-1-yl}-pyridin-3-yl)-isonicotinamide.

Step A: piperazine (1.38 g) was added to a stirred solution of2,6-dichloro-3-nitropyridine (3.0 g, prepared according to J.Heterocyclic Chem. 1994, 31, 73) and diisopropylethylamine (3.0 ml) indichloromethane (100 ml) at 0° C. under N₂. The resulting solution wasstirred at room temperature for 2 hours then poured into saturatedaqueous sodium bicarbonate, extracted with dichloromethane, dried oversodium sulfate and concentrated in vacuo. The residue was subjected tosilica gel chromatography (ethyl acetate:methanol 8:2) to afford1-(6-Chloro-3-nitro-pyridin-2-yl)-piperazine (2.99 g) as a red solid.M.p. 50-53° C.; MS (ES+) 243/245 (M+H⁺).

Step B: The product obtained in Step A (800 mg) was dissolved inacetonitrile (320 ml), diisopropylethylamine (1.2 ml) and4-trifluoromethylcinnamyl chloride (728 mg) were added. The solution wasstirred at room temperature for 24 hours, the solvent was removed invacuo and the residue was subjected to silica gel chromatography(cyclohexane:ethyl acetate 7:3) to afford1-(5-Chloro-3-nitro-pyridin-2-yl)-4-[(E)-3-(4-trifluoromethyl-phenyl)-allyl]-piperazine(0.79 g) as a yellow foam. M.p. 129-132° C.; ¹H NMR (400 MHz, CDCl₃) 2.7(m, 4H), 3.3 (d, J=9 Hz, 1H), 3.5 (m, 4H), 6.3 (dt, J=18, 9 Hz, 1H), 6.5(d, J=18 Hz, 1H), 7.4 (m, 4H), 8.2 (d, J=2 Hz, 1H), 8.3 (d, J=2 Hz, 1H);MS (ES+) 427/429 (M+H⁺).

Step C: The product obtained in Step B (435 mg) was reduced and acylatedas described in Example 1 Step B and C to afford after silica gelchromatography (cyclohexane:ethyl acetate 7:3) the title product (185mg). M.p. 156-159° C.; ¹H NMR (400 MHz, CDCl₃) 2.7 (m, 4H), 3.1 (m, 4H),3.2 (d, J=9 Hz, 2H), 6.3 (dt, J=18, 9 Hz, 1H), 6.5 (d, J=18 Hz, 1H), 7.4(d, J=9 Hz, 2H), 7.45 (d, J=9 Hz, 2H), 7.5 (d, J=5 Hz, 1H), 7.6 (s, 1H),8.0 (d, J=1.5 Hz, 1H), 8.55 (d, J=5 Hz, 1H), 8.65 (d, J=1.5 Hz, 1H), 8.8(s, 1H, NH); HPLC Retention Time 2.12 min; MS (ES+) 536/538 (M+H⁺).

The following compounds were prepared according to procedures analogousto those described in Example 6:

Retention M.p Time Compound Name Structure (° C.) MH⁺ (min)2-chloro-N-(2- {4-[(E)-3-(4- chloro-phenyl)- allyl]-piperazin-1-yl}-pyridin-3- yl)- isonicotinamide

106-109 468/470 2.05 2-chloro-N-(2- {4-[(E)-3-(4- trifluoromethoxy-phenyl)-allyl]- piperazin-1-yl}- pyridin-3-yl)- isonicotinamide

518/520 2.19 2-chloro-N-(6- chloro-2-{4-[(E)- 3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- pyridin-3-yl)- isonicotinamide

 70-73 502/504 2.16 2-chloro-N-(5- chloro-2-{4-[(E)- 3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- pyridin-3-yl)- isonicotinamide

127-129 502/504 2.29 2-chloro-N-(5- chloro-2-{4-[(E)- 3-(4-trifluoromethoxy- phenyl)-allyl]- piperazin-1-yl}- pyridin-3-yl)-isonicotinamide

115-117 552/554 2.40 2-chloro-N-(6- methyl-2-{4-[(E)- 3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- pyridin-3-yl)- isonicotinamide

 67-70 482/484 2.44 2-Chloro-N-(4- chloro-6-{4-[(E)- 3-(4-chloro-phenyl)-allyl]- piperazin-1 -yl}- pyrimidin-5-yl)- isonicotinamide

 84-87 503/505 2.48 2-Chloro-N-(4- {4-[(E)-3-(4- chloro-phenyl)-allyl]-piperazin- 1-yl}-pyridin-3- yl)- isonicotinamide

 77-79 468/470 1.99

EXAMPLE 7

This Example illustrates the preparation of2-chloro-N-(2-chloro-4-{4-[(E)-3-(4-trifluoromethoxy-phenyl)-allyl]-piperazin-1-yl}-pyrimidin-5-yl)-isonicotinamide.

1-t-Butoxycarbonyl-piperazine (2.36 g) was condensed with2,4-dichloro-pyrimidin-5-ylamine (2.0 g) in dimethylsulfoxide (20 ml) inthe presence of triethylamine (5.3 ml) according to the method describedin Example 1, Step A.4-(5-Amino-2-chloro-pyrimidin-4-yl)-piperazine-1-carboxylic acidtert-butyl ester (3.4 g) was obtained as violet crystals. MS (ES+)314/316 (M+H⁺). The title product (120 mg) was obtained from thisintermediate according to the methods described in Example 1, step C andD.2-Chloro-N-(2-chloro-4-{4-[(E)-3-(4-trifluoromethoxy-phenyl)-allyl]-piperazin-1-yl}-pyrimidin-5-yl)-isonicotinamide.M.p. 210-211° C.; ¹H NMR (400 MHz, CDCl₃) 2.5 (m, 4H), 3.1 (d, J=9 Hz,1H), 3.6 (m, 4H), 6.1 (dt, J=18, 9 Hz, 1H), 6.4 (d, J=18 Hz, 1H), 7.1(d, J=11 Hz, 2H), 7.3 (d, J=11 Hz, 2H), 7.6 (d, J=5 Hz, 1H), 7.7 (s,1H), 7.8 (s, 1H, NH), 8.4 (s, 1H), 8.5 (d, J=5 Hz, 1H); MS (ES+) 553/555(M+H⁺).

The following compounds were prepared according to procedures analogousto those described in Example 7:

Retention M.p Time Compound Name Structure (° C.) MH⁺ (min)2-chloro-N-(2- chloro-4-{4-[(E)-3- (4-chloro-phenyl)-allyl]-piperazin-1- yl}-pyrimidin-5-yl)- isonicotinamide

187-189 503/505 2.09 2-chloro-N-(2- chloro-4-{4-[(E)-3-(4-trifluoromethyl- phenyl)-allyl]- piperazin-1-yl)- pyrimidin-5-yl)-isonicotinamide

169-173 537/539 2.21

EXAMPLE 8

This Example illustrates the preparation of2-Chloro-N-(5-{4-[(E)-3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}-1,3-dimethyl-1H-pyrazol-4-yl)-isonicotinamide.

Step A: A solution of N—BOC-piperazine (4.3 g) and triethylamine (9 ml)in dimethylsulfoxide (40 ml) at 0° C. under nitrogen was treated with4-chlorocinnamyl chloride (5 g) and the resulting solution was stirredat room temperature for 18 hours, poured into water, extracted withethyl acetate (three times), dried over sodium sulfate and concentratedin vacuo. The residue was filtered over silica gel to afford crude4-[(E)-3-(4-Chloro-phenyl)-allyl]-piperazine-1-carboxylic acidtert-butyl ester. This compound was dissolved in dichloromethane (30 ml)and treated with trifluoroacetic acid (10 ml) at room temperature for 18hours. Concentration afforded1-[(E)-3-(4-Chloro-phenyl)-allyl]-piperazine (5.8 g), which wascharacterised by its mass and NMR spectra. MS (ES+) 151/153(M-piperazine), 237/239 (M+H⁺).

Step B: The product obtained in Step A (3.1 g) was condensed with5-Chloro-1,3-dimethyl-4-nitro-1H-pyrazole (1.5 g) in dimethylsulfoxide(20 ml) in the presence of triethylamine (3.4 ml) as described inExample 1, Step A to afford1-[(E)-3-(4-Chloro-phenyl)-allyl]-4-(2,5-dimethyl-4-nitro-2H-pyrazol-3-yl)-piperazine(1.82 g) as a brown solid. ¹H NMR (400 MHz, CDCl₃) 2.4 (s, 3H), 2.6 (m,4H), 3.2 (m, 6H), 3.7 (s, 3H), 6.3 (dt, J=18, 9 Hz, 1H), 6.5 (d, J=18Hz, 1H), 7.2-7.3 (m, 4H); MS (ES+) 151/153, 376/378 (M+H⁺).

Step C: To a solution of the product obtained in Step B (800 mg) intetrahydrofuran (8 ml) and methanol (8 ml) at room temperature undernitrogen was added tin(II) chloride monohydrate (2.9 g) and sodiumacetate trihydrate (3.5 g). The resulting mixture was stirred at roomtemperature for 34 hours. The reaction mixture was partitioned between1M sodium hydroxide and ethyl acetate, stirred for 10 min, the organiclayer was separated, dried over sodium sulfate and concentrated.1-[(E)-3-(4-Chlorophenyl)-allyl]-4-(2,5-dimethyl-4-amino-2H-pyrazol-3-yl)-piperazine(510 mg) was obtained as a red solid. ¹H NMR (400 MHz, CDCl₃) 2.3 (s,3H), 2.8 (m, 4H), 3.3 (m, 4H), 3.4 (d, J=9 Hz, 2H), 3.8 (s, 3H), 6.4(dt, J=18, 9 Hz, 1H), 6.7 (d, J=18 Hz, 1H), 7.3-7.4 (m, 4H); MS (ES+)151/153 (cinnamyl), 196(M-cinnamyl), 346/348 (M+H⁺).

Step D: triethylamine (0.46 ml) was added to a stirred solution of thecompound obtained in Step C (250 mg) in dichloromethane (10 ml); thesolution was cooled to 0° C. and 2-chloroisonicotinoyl chloride (250 mg)was added. The resulting mixture was stirred at room temperature for 12hours, poured into water, extracted two times with dichloromethane, thecombined organic layers were dried over sodium sulfate and concentratedin vacuo. The residue was subjected to silica gel chromatography (ethylacetate:ethanol 9:5) to afford the title compound (158 mg). M.p. 85-88°C.; ¹H NMR (400 MHz, CDCl₃) 2.0 (s, 3H), 2.52 (br s, 4H), 3.05 (t, J=4.8Hz, 4H), 3.1 (d, J=6.8 Hz, 2H), 3.58 (s, 3H), 6.13 (dt, J=15.6, 6.8 Hz,1H), 6.40 (d, J=15.6 Hz, 1H), 7.20 (s, 4H), 7.55 (d, J=5.2 Hz, 1H), 7.69(s, 1H), 8.49 (d, J=5.2 Hz, 1H); Retention Time LCMS 2.26 min; MS (ES+)485/487 (M+H⁺).

The following compounds were prepared according to procedures analogousto those described in Example 8:

Retention M.p Time Compound Name Structure (° C.) MH⁺ (min)2-Chloro-N-(2-{4- [(E)-3-(4-chloro- phenyl)-allyl]- piperazin-1-yl}-6-methoxy-pyridin-3- yl)-isonicotinamide

65-69 498/500 2.39

EXAMPLE 9

This Example illustrates the preparation of2-Chloro-N-(2-{4-[(E)-3-(4-chloro-phenyl)-allyl]-2-oxo-piperazin-1-yl}-4-fluoro-phenyl)-isonicotinamide.

Step A: piperazinone was prepared according to the method described inU.S. Pat. No. 6,433,134: ethyl chloroformate (10 g) in ethanol (50 ml)was added dropwise to a solution of ethylene diamine (32.85 ml) inethanol (150 ml) at room temperature under nitrogen. The resultingsolution was stirred at room temperature for 48 hrs, then treateddropwise over 30 min with a freshly prepared solution of sodiumethanolate in ethanol (prepared from 1.9 g sodium and 90 ml ethanol).The solution was stirred at room temperature for 2 hours, filtered onHyflo (rinsed with ethanol), then the solvent and the excess diaminewere removed in vacuo. The oily residue was refluxed in toluene (400 ml)for 3 hours, the toluene layer decanted and separated from the remainingoil; the toluene layer was kept at 0° C. overnight and the solidcollected by filtration to afford piperazinone (3.6 g). M.p. 108-109° C.

Step B: piperazinone (3.6 g) was dissolved in acetonitrile (100 ml) thentreated with diisopropylethylamine (9 ml) and 4-chlorocinnamyl chloride(6.7 g). The resulting reaction mixture was stirred at room temperatureunder nitrogen for 48 hours. The white precipitate was collected byfiltration, washed with cold acetonitrile and dried under vacuum (whitesolid, 4.35 g). The filtrate was concentrated in vacuo and the residuecrystallized from acetonitrile (white crystals, 1.4 g). M.p. 129-130° C.Both fractions showed satisfactory analytical data:N-4-[(E)-3-(4-chloro-phenyl)-allyl]-piperazin-2-one. ¹H NMR (400 MHz,CDCl₃) 2.63 (t, J=5 Hz, 2H), 3.12 (s, 2H), 3.15 (d, J=7 Hz, 2H), 3.32(m, 2H), 6.1 (dt, J=18, 9 Hz, 1H), 6.5 (d, J=18 Hz, 1H), 7.2-7.3 (m,4H).

Step C: To a solution of the product obtained in Step B (2.51 g) indimethylformamide (50 ml) at room temperature under nitrogen was addedpotassium carbonate (3.45 g) and 2,4-difluoronitrobenzene (1.59 g). Theresulting mixture was stirred at 100° C. for 24 hours. Potassiumcarbonate (1.4 g) and 2,4-difluoronitrobenzene (1.4 g) were added againand the resulting mixture stirred at 110° C. for 48 hours. The reactionmixture was cooled to room temperature, poured into water, extractedthree times with ethyl acetate; the combined organic layers were washedwith brine, dried (Na₂SO₄) and concentrated in vacuo. Columnchromatography (cyclohexane/ethyl acetate 6:4) afforded4-[(E)-3-(4-chloro-phenyl)-allyl]-1-(5-fluoro-2-nitro-phenyl)-piperazin-2-one(1.9 g) as a brown solid. M.p. 57° C.; MS (ES+) 151/153 (cinnamyl),390/392 (M+H⁺).

Step D: Raney nickel (50% slurry in water, 200 mg) was added to asolution of the compound obtained in Step C (389 mg) in ethanol (10 ml);hydrazine hydrate (0.5 ml) was added and the reaction mixture wasstirred at room temperature until gas evolution ceased (1 hour). Thereaction mixture was filtered over Hyflo, the solvent removed in vacuoand the residue purified by column chromatography (2.5% methanol inethyl acetate) to afford1-(2-Amino-5-fluoro-phenyl)-4-[(E)-3-(4-chloro-phenyl)-allyl]-piperazin-2-one(162 mg). Retention Time LCMS 2.81 min; MS (ES+) 360/362 (M+H⁺).

Step E: triethylamine (0.14 ml) was added to a stirred solution of thecompound obtained in Step D (140 mg) in dichloromethane (10 ml); thesolution was cooled to 0° C. and 2-chloroisonicotinoyl chloride (200 mg)was added. The resulting mixture was stirred at room temperature for 3hours, poured into water, extracted two times with dichloromethane, thecombined organic layers were dried over sodium sulfate and concentratedin vacuo. The residue was subjected to silica gel chromatography (ethylacetate:cyclohexane 1:1) to afford the title compound as a white powder(130 mg). M.p. 75-77° C.; Retention Time LCMS 3.46 min; MS (ES+)150/152, 499/501 (M+H¹).

EXAMPLE 10

This Example illustrates the preparation of2-chloro-N-(2-{4-[(E)-3-(4-chloro-phenyl)-allyl]-piperazin-1-yl}-4,6-dichloro-phenyl)-isonicotinamide.

Step A: A solution of 1,3,5-trichloronitrobenzene (800 mg) and1-t-butoxycarbonyl-piperazine (790 mg) in toluene (20 ml) was stirred at80° C. under N₂ for 15 hours. The reaction mixture was cooled to roomtemperature, partitioned between water and ethyl acetate, the organiclayer was dried (Na₂SO₄) and concentrated in vacuo. The residue wassubjected to silica gel chromatography (cyclohexane:ethyl acetate 8:2)to afford 4-(3,5-dichloro-2-nitrophenyl)-piperazine-1-carboxylic acidtert-butyl ester (0.37 g). ¹H NMR (400 MHz, CDCl₃) 1.5 (s, 9H), 2.9 (m,4H), 3.5 (m, 4H), 7.0 (d, J=2 Hz, 1H), 7.16 (d, J=2 Hz, 1H); RetentionTime HPLC 2.33 min; MS (ES+) 276/278 (M-BOC), 317/319 (M-isoprene).

Step B: The product obtained in Step A (200 mg) was reduced with tinchloride then acylated with 2-chloroisonicotinoyl chloride as describedin example 8, step C and D to afford4-{2-[(2-Chloro-pyridine-4-carbonyl)-amino]-3,5-dichloro-phenyl}-piperazine-1-carboxylicacid tert-butyl ester (1.04 g). Retention Time HPLC 2.05 min; MS (ES+)431/433, 485/487/489 (MH⁺).

Step C: A solution of the compound obtained in Step C (0.08 g) indichloromethane (1 ml) was treated with trifluoroacetic acid (0.1 ml)for 24 hours at room temperature. The reaction mixture was concentratedin vacuo. The residue was dissolved in acetonitrile (1 ml),diisopropylethylamine (0.15 ml) and 4-chlorocinnamyl chloride (0.05 g)were added. The solution was stirred 24 hours at room temperature, thesolvent was removed in vacuo and the residue was subjected to silica gelchromatography to afford the title product (66 mg) as a solid. M.p.79-80° C.; ¹H NMR (400 MHz, CDCl₃) 2.37 (m, 4H), 2.6 (m, 4H), 3.1 (d,J=9 Hz, 2H), 6.2 (dt, J=18, 9 Hz, 1H), 6.5 (d, J=18 Hz, 1H), 6.9 (d, J=2Hz, 1H), 7.2-7.3 (m, 5H), 7.5 (s, 1H, NH), 7.6 (d, J=4.5 Hz, 1H), 7.7(s, 1H), 8.5 (d, J=5.5 Hz, 1H); Retention Time HPLC 1.44 min; MS (ES+)535/537/539 (M+H¹).

The following compounds were prepared according to procedures analogousto those describer) in Example 10:

Retention M.p Time Compound Name Structure (° C.) MH⁺ (min)2-chloro-N-(2-{4- [(E)-3-(4-chloro- phenyl)-allyl]- piperazin-1-yl}-4,5-difluoro- phenyl)- isonicotinamide

 55-58 503-505 1.62 2-chloro-N-(2-{4- [(E)-3-(4-chloro- phenyl)-allyl]-piperazin-1-yl}-4- chloro-5-fluoro- phenyl)- isonicotinamide

122-123 519 1.52 2-chloro-N-(2-{4- [(E)-3-(4-chloro- phenyl)-allyl]-piperazin-1-yl}- 4,5-dichloro- phenyl)- isonicotinamide

154-155 535/537/539 1.57 2-chloro-N-(2-{4- [(E)-3-(4-chloro-phenyl)-allyl]- piperazin-1-yl}- 4,5,6-trifluoro- phenyl)-isonicotinamide

 94-96 521/523 1.39 2-chloro-N-(2-{4- [(E)-3-(4-chloro- phenyl)-allyl]-piperazin-1-yl}- 3,4,6-trifluoro- phenyl)- isonicotinamide

 80-82 521/523 1.36

EXAMPLE 11

This Example illustrates the pesticidal/insecticidal properties ofcompounds of formula (I).

Test against were performed as follows:

Spodoptera littoralis (Egyptian cotton leafworm)

Cotton leaf discs were placed on agar in a 24-well microtiter plate andsprayed with test solutions at an application rate of 200 ppm. Afterdrying, the leaf discs were infested with 5 L₁ larvae. The samples werechecked for mortality, repellent effect, feeding behaviour, and growthregulation 3 days after treatment (DAT). The following compounds gave atleast 80% control of Spodoptera littoralis:

I-3, I-26, I-29, I-30, I-49, I-52, I-53, I-75, I-417, I-532, I-578,I-785, I-854, I-877, II-49, III-49, V-49, XII-49, XIV-26, XV-26, XXIV-2,XXIV-46, XXIV-90, XXIV-93, XXIV-94, XXV-26 and XXV-49.

Heliothis virescens (Tobacco budworm):

Eggs (0-24 h old) were placed in 24-well microtiter plate on artificialdiet and treated with test solutions at an application rate of 200 ppmby pipetting. After an incubation period of 4 days, samples were checkedfor egg mortality, larval mortality, and growth regulation. Thefollowing compounds gave at least 80% control of Heliothis virescen:

I-3, I-6, I-7, I-26, I-29, I-30, I-47, I-49, I-52, I-53, I-72, I-75,I-417, I-532, I-578, I-785, I-854, I-877, III-49, V-49, XII-49, XIV-26,XIV-49, XV-26, XVI-26, XVII-26, XXIV-2, XXIV-46, XXIV-90, XXIV-93,XXIV-94, XXV-2, XXV-26, XXV-49 and XXV-68.

Plutella xylostella (Diamond back moth):

24-well microtiter plate (MTP) with artificial diet was treated withtest solutions at an application rate of 18.2 ppm by pipetting. Afterdrying, the MTP's were infested with larvae (L2)(10-15 per well). Afteran incubation period of 5 days, samples were checked for larvalmortality, antifeedant and growth regulation. The following compoundsgave at least 80% control of Plutella xylostella:

I-26, I-29, I-30, I-49, I-417, I-532, I-578, I-785, I-854, I-877, V-49,IX-49, XII-49, XIV-26, XV-26, XXIV-46, XXIV-90 and XXV-26.

Aedes aegypti (Yellow fever mosquito):

10-15 Aedes larvae (L2) together with a nutrition mixture are placed in96-well microtiter plates. Test solutions at an application rate of 2ppm are pipetted into the wells. 2 days later, insects were checked formortality and growth inhibition. The following compounds gave at least80% control of Aedes aegypti

I-3, I-26, I-29, I-30, I-49, I-52, I-53, I-72, I-75, I-76, III-49,III-118, XIV-26, XV-26, XXIV-2, XXIV-46, XXIV-90, XXIV-93, XXIV-94 andXXV-68.

Myzus persicae (Green peach aphid):

Sunflower leaf discs were placed on agar in a 24-well microtiter plateand sprayed with test solutions at an application rate of 200 ppm. Afterdrying, the leaf discs were infested with an aphid population of mixedages. After an incubation period of 6 DAT, samples were checked formortality. The following compounds gave at least 80% control of Myzuspersicae:

I-3, I-26, I-29, I-26, I-29, I-30, I-49, I-52, I-53, I-72, I-75, III-49,V-49, XXIV-46, XXIV-90 and XXIV-94.

The invention claimed is:
 1. A compound of formula I′

wherein Y is a single bond, C═O, C═S or S(O)_(m) where m is 0, 1 or 2;the ring

is a benzene or pyridine ring; R¹ is C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆alkoxy(C₁₋₆)alkyl, heteroaryl(C₁₋₃)alkyl (wherein the heteroaryl groupmay be optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylsulfonyl, C₁₋₆alkoxycarbonyl, or two adjacent positions on the heteroaryl system maybe cyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclicring, itself optionally substituted with halogen), phenyl(C₁₋₃)alkyl(wherein the phenyl group may be optionally substituted by halogen, C₁₋₄alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl,heteroaryl, amino, dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆alkoxycarbonyl, or two adjacent positions on the phenyl ring may becyclised to form a 5, 6 or 7 membered carbocyclic or heterocyclic ring,itself optionally substituted with halogen), phenyl (which may beoptionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino,dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl, or two adjacentpositions on the phenyl ring may be cyclised to form a 5, 6 or 7membered carbocyclic or heterocyclic ring, itself optionally substitutedwith halogen), heteroaryl (which may be optionally substituted by halo,nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy,C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl, or two adjacent positions onthe heteroaryl system may be cyclised to form a 5, 6 or 7 memberedcarbocyclic or heterocyclic ring, itself optionally substituted withhalogen), C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₂₋₆ alkenyl, heterocyclyl(optionally substituted by halo, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆alkoxy or C₁₋₆ haloalkoxy), C₁₋₆ alkylthio, C₁₋₆ haloalkylthio orNR¹³R¹⁴ where R¹³ and R¹⁴ are independently hydrogen, C₁₋₆ alkyl or C₁₋₆haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₂₋₆ alkylcarbonyl, phenylcarbonyl,(where the phenyl is optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl,amino or dialkylamino), phenyl(C₁₋₃)alkyl (wherein the phenyl group maybe optionally substituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl, heteroaryl, amino,dialkylamino, C₁₋₆ alkylsulfonyl, C₁₋₆ alkoxycarbonyl, or two adjacentpositions on the phenyl ring may be cyclised to form a 5, 6 or 7membered carbocyclic or heterocyclic ring, itself optionally substitutedwith halogen) or heteroaryl(C₁₋₃)alkyl (wherein the heteroaryl group maybe optionally substituted by halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆haloalkyl, C₁₋₆ alkoxy, C₁₋₆ haloalkoxy, C₁₋₆ alkylsulfonyl, C₁₋₆alkylsulfinyl, C₁₋₆ alkylthio, C₁₋₆ alkoxycarbonyl, C₁₋₆alkylcarbonylamino, arylcarbonyl, or two adjacent positions on theheteroaryl system may be cyclised to form a 5, 6 or 7 memberedcarbocyclic or heterocyclic ring, itself optionally substituted withhalogen); R² is H or C₁-C₄ alkyl; or R¹ and R² together with the groupsY and N form a 5- or 6-membered heterocyclic ring which may optionallycontain one further heteroatom selected from O, N or S and which may beoptionally substituted by C₁₋₄ alkyl, C₁₋₄ haloalkyl or halogen; each R⁴is independently halogen, cyano, C₁₋₈ alkyl, C₁₋₈ haloalkyl, C₁₋₈cyanoalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₂₋₆ alkenyl,trimethylsilyl(C₂₋₆)alkynyl, C₁₋₆ alkoxycarbonyl, C₃₋₇ cycloalkyl, C₁₋₃alkyl (C₃₋₇) cycloalkyl, phenyl (optionally substituted by halogen, C₁₋₄alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN, NO₂, aryl,heteroaryl, amino or dialkylamino), heterocyclyl (optionally substitutedby halo, nitro, cyano, C₁₋₆ alkyl, C₁₋₆ haloalkyl, C₁₋₆ alkoxy or C₁₋₆haloalkoxy), C₁₋₈ alkoxy, C₁₋₆ haloalkoxy, phenoxy (optionallysubstituted by halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄haloalkoxy, CN, NO₂, aryl, heteroaryl, amino or dialkylamino),heteroaryloxy (optionally substituted by halo, nitro, cyano, C₁₋₃ alkyl,C₁₋₃ haloalkyl, C₁₋₃ alkoxy or C₁₋₃ haloalkoxy), di(C₁₋₈)alkylamino, or2 adjacent groups R⁴ together with the carbon atoms to which they areattached form a 4, 5, 6 or 7 membered carbocylic or heterocyclic ringwhich may be optionally substituted by halogen; n is 0, 1, 2 or 3; R⁸ is—C(R⁵¹)(R⁵²)—[CR⁵³═CR⁵⁴]z-R⁵⁵ where z is 1 or 2, R⁵¹ and R⁵² are eachindependently H or C₁₋₂ alkyl, R⁵³ and R⁵⁴ are each independently H,halogen, C₁₋₄ alkyl or C₁₋₄ haloalkyl and R⁵⁵ is phenyl substituted byhalogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy, CN,NO₂, aryl, heteroaryl, amino or dialkylamino or heteroaryl substitutedby halogen, C₁₋₄ alkyl, C₁₋₄ alkoxy, C₁₋₄ haloalkyl, C₁₋₄ haloalkoxy,CN, NO₂, aryl, heteroaryl, amino or dialkylamino; each Ra isindependently halogen, hydroxy, cyano, optionally substituted C₁₋₈alkyl, optionally substituted C₂₋₆ alkenyl, optionally substituted C₂₋₆alkenyl, optionally substituted alkoxycarbonyl, optionally substitutedalkylcarbonyl, optionally substituted alkylaminocarbonyl, optionallysubstituted dialkylaminocarbonyl, optionally substituted C₃₋₇cycloalkyl, optionally substituted aryl, optionally substitutedheteroaryl, optionally substituted heterocyclyl, optionally substitutedalkoxy, optionally substituted aryloxy, optionally substitutedheteroaryloxy, optionally substituted alkylthio, optionally substitutedarylthio or R²³R²⁴N where R²³ and R²⁴ are, independently, hydrogen, C₁₋₈alkyl, C₃₋₇ cycloalkyl, C₃₋₆ alkenyl, C₃₋₆ alkenyl, C₃₋₇cycloalkyl(C₁₋₄)alkyl, C₂₋₆ haloalkyl, C₁₋₆ alkoxy(C₁₋₆)alkyl, C₁₋₆alkoxycarbonyl or R²³ and R²⁴ together with the N atom to which they areattached form a five, six or seven-membered heterocyclic ring which maycontain one or two further heteroatoms selected from O, N or S and whichmay be optionally substituted by one or two C₁₋₆ alkyl groups, or two Ragroups attached to the same carbon atom are ═O, ═S, ═NRb, ═CRcRd whereRb, Rc and Rd are independently H or optionally substituted alkyl; and pis 0, 1, 2, 3 or 4; or salts or N-oxides thereof.
 2. A compound offormula

wherein R⁴, R⁸, Ra, T, Y, n and p are as defined in relation to formulaI′ in claim
 1. 3. A compound of formula

wherein R⁴, R⁸, Ra, T, Y, n and p are as defined in relation to formulaI′ in claim
 1. 4. An insecticidal, acaricidal or nematicidal compositioncomprising an insecticidally, acaricidally or nematicidally effectiveamount of a compound of formula I′ as defined in claim 1.